Protective layer compositions and their use, electronic devices and methods of manufacturing the same

Abstract

The application provides a protective layer composition and application thereof. The protective layer composition comprises polyetherimide and an organic solvent, the polyetherimide comprises etherimide repeating units derived from a diamine and an aromatic diether anhydride; and the content of metal ions in the protective layer composition is less than 10 ppb. The protective layer composition can reduce the metal pollution caused by metal-based patterning materials or supporting layer materials of the metal-based patterning materials to a non-patterning area of a substrate during the formation of a patterned film, and the protective layer composition can be removed more easily subsequently, thereby improving the production yield and performance reliability of electronic devices.

Description

TECHNICAL FIELD

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

[0002] The preparation process of an electronic device usually involves a patterning process. Among them, the patterning compositions used for forming a patterned film mainly include a chemical amplification type organic resin patterning composition and a metal element-containing patterning composition, and the latter exhibits obvious advantages in forming a pattern with a small feature size.

[0003] However, in the coating process of a metal-based patterning composition containing a metal element or a supporting layer material (such as a metal hard mask material for improving the resolution of a pattern formed by the metal-based patterning composition) on a substrate (such as a wafer), the metal-based patterning composition or the supporting layer material will flow to the edge of the substrate, resulting in that the edge of the substrate is easily contaminated by the metal element, and further affecting the yield and reliability of the electronic device prepared.

[0004] In order to reduce the above-mentioned metal contamination problem, the industry mainly adopts the following strategy: coating a protective material with a certain thickness on the edge of the substrate, then spin-coating a metal-based patterning composition on one side surface of the substrate, then removing at least a part of the metal-based patterning composition or the supporting layer material in contact with the protective material by using a edge cleaning agent, and then removing the above-mentioned protective material after the metal-based patterning material or the supporting layer material is converted into a patterned film by exposure and development. In theory, the above-mentioned protective material needs to meet many requirements, such as good resistance to solvents and developers in the metal-based patterning composition, not significantly dissolved in the edge cleaning agent, and quickly removed by a specific solvent. However, few of the actual protective materials used on the edge of the substrate can simultaneously meet the above-mentioned requirements, resulting in that the ability of the protective material to prevent metal contamination is very low or even fails. SUMMARY

[0005] In view of this, the embodiments of the present application provide a protective layer composition capable of effectively reducing metal contamination of a substrate in an electronic device manufacturing process, and application thereof, an electronic device and a manufacturing method thereof.

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

[0007] The protective layer composition containing the polyetherimide described above has a high selective chemical etching rate, has no significant dissolution characteristics in solvents, edge-bead removers, and developers in the metal-based patterning composition, and can be quickly removed by a specific solvent, so that the protective layer composition can be disposed on the edge of the substrate and can stably exist on the edge of the substrate during coating and development of the metal-based patterning composition, reduces / prevents metal ions in the metal-based patterning composition from polluting the edge of the substrate, and does not damage the metal-based patterning film during its removal, thereby ensuring yield and performance reliability of the electronic device prepared. In addition, the metal ion content of the protective layer composition described above is less than or equal to 10 ppb, which can ensure that it can be practically used for anti-metal contamination protection on the edge of the substrate. Similarly, the protective layer composition can also reduce metal contamination caused by the supporting layer material of the metal-based patterning composition.

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

[0009]

[0010] wherein T is -O- or -O-Z-O-, Z is selected from a divalent group containing at least one aromatic ring, R is selected from a C 2-20 divalent hydrocarbon group with or without heteroatoms. The polyetherimide having the etherimide repeating unit shown in formula (I) has high solubility in aromatic solvents and good chemical corrosion resistance in aliphatic solvents, so that the protective layer material containing the polyetherimide has a very low degree of dissolution during coating, edge-bead removal, and development of the metal-based patterning composition, and can better play a role in reducing metal contamination of the substrate.

[0011] Further, in some embodiments of the present application, Z comprises a structure as shown in formula (1):

[0012]

[0013] wherein a, b, c are independently selected from an integer from 0 to 4, R 1 , R 2 are independently selected from one or more of a halogen atom, a halogenated or unhalogenated C 1-10 alkyl group, a halogenated or unhalogenated C 1-10 alkoxy group; X is selected from one of a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, a C 1-18 divalent hydrocarbon group with or without heteroatoms; and the position marked with * is a connecting position.

[0014] In some embodiments of the present application, a = 0, b = 0, and c = 1; X is selected from -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, halogenated or unhalogenated C 1-5 In some embodiments of the present application, the polyetherimide has repeating units of formula (I) and repeating units of formula (II):

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

[0016]

[0017] wherein d, e are independently selected from an integer from 0 to 4, and f is 0 or 1; L1, L2 are independently selected from a single bond or C 1-6 alkylene; R 3 , R 4 each occurrence is independently selected from a halogen atom, halogenated or unhalogenated C 1-10 alkyl, halogenated or unhalogenated C 1-10 alkylene; Q is selected from a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, halogenated or unhalogenated C 1-5 alkylene; the position marked with * is a connecting position.

[0018] In some embodiments of the present application, the polyetherimide further includes imide repeating units derived from a diamine and an aromatic dianhydride not containing ether oxygen linkage. 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 units independently include one or more of structures of formula (II), formula (III), and formula (IV):

[0020]

[0021] wherein R is selected from one or more of an alkylene group with or without heteroatoms, a cycloalkylene group with or without heteroatoms, and an arylene group with or without heteroatoms; W does not contain ether oxygen linkage.

[0022] In some embodiments 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 to 10 g / min measured at 340°C to 370°C;

[0024] (b) the polyetherimide has an intrinsic viscosity of a m-cresol solution thereof at 25°C 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 some embodiments of the present application, the polyetherimide has a weight average molecular weight in the range of 1000-150000. The weight average molecular weight of the polyetherimide is in the appropriate range, which is conducive to regulating the solubility of the protective layer containing the same in different solvents.

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

[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 of the first film immersed in methyl isobutyl carbinol is less than the thickness loss rate of the first film immersed 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 of the second film immersed in methyl isobutyl carbinol is less than the thickness loss rate of the second film immersed in anisole is greater than

[0029] Regulating the film thickness loss rate of the first polyetherimide film with low molecular weight and the second polyetherimide film with high molecular weight in different solvents to meet the above requirements can better ensure that the dry film of the protective layer composition containing the first polyetherimide and the second polyetherimide has better resistance to fatty ketone solvents, fatty alcohol solvents and the like, and can be quickly removed by benzyl anisole.

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

[0031] The second aspect of the embodiments of the present application provides an application of the protective layer composition as described in the first aspect of the present application to reduce metal contamination in a non-pattern area in a patterning process.

[0032] The protective layer composition is arranged at the edge of the substrate to be subjected to the patterning process, and the protective layer material formed after the solvent volatilizes can prevent the metal-based patterning material or the supporting layer material thereof from flowing to the edge of the substrate to directly contact the edge of the substrate, thereby playing a role of resisting metal contamination.

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

[0034] applying the protective layer composition as described in the first aspect of the present application to the edge of the substrate to form a protective layer;

[0035] applying a metal-based patterning material to one side surface of the substrate to form a film layer of the metal-based patterning material on the substrate and the protective layer;

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

[0037] sequentially exposing and developing the film layer of the metal-based patterning material left on the substrate to form a metal-based patterning film on the substrate;

[0038] after the developing, removing the protective layer.

[0039] In the manufacturing method of the electronic device, the protective layer composition of the embodiments of the present application is used to protect the edge of the substrate, which can stably exist during the formation of the metal-based patterning film, can reduce the metal contamination of the metal-based patterning material to the non-pattern area (such as the edge of the substrate) of the substrate, and can be easily removed after the formation of the metal-based patterning film, thereby improving the preparation yield and performance reliability of the electronic device.

[0040] The fourth aspect of the embodiments of the present application further provides an electronic device manufactured by the manufacturing method as described in the third aspect of the embodiments of the present application. BRIEF DESCRIPTION OF DRAWINGS

[0041] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description are only some embodiments of the present application, and those skilled in the art can also obtain other drawings according to these drawings without any creative effort.

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

[0043] The embodiments of the present application will be described below with reference to the accompanying drawings.

[0044] The patterning process generally includes the following steps: (1) applying a patterning composition on a substrate to form a film layer of patterning material by heating; (2) selectively exposing the film layer of patterning material to an exposure source through a mask with a predetermined pattern, so that the solubility of the exposed area and the unexposed area to a developer is different; (3) developing the exposed film layer of patterning material with the developer, so as to leave a patterning film with the same or opposite pattern of the mask on the substrate, and using the patterning film as a mask to selectively etch the substrate, so as to finally achieve the desired pattern on the substrate.

[0045] In order to form a patterning film with small feature size, the patterning composition used in the current patterning process is mostly metal-based patterning composition containing metal elements, such as metal oxide resist (MOR). After applying the metal-based patterning composition on a predetermined area of one side surface of the substrate, it will generally flow to the edge of the substrate (including the side surface and even the back surface of the substrate, etc.), which will cause the non-predetermined area of the substrate to be contaminated by metal ions in the metal-based patterning composition, and further affect the product yield and performance reliability of the electronic device made of the substrate.

[0046] In order to reduce the above-mentioned metal contamination problem caused by the metal-based patterning material, Figure 1 An exemplary flowchart of the current patterning process is shown. Figure 1 A1 shows a commonly used substrate—wafer structure. A2 shows a schematic diagram of applying a wafer protective layer (EPL) material (dark gray part) on the edge of the wafer by edge coating. A3 shows that the residual solvent in the EPL material is further removed by heating treatment. A4 shows that a metal-based patterning composition is spin-coated on one side surface of the wafer to form a film layer of metal-based patterning material. Figure 1 In A4, the metal-based patterning material (light gray part) covers one side surface of the wafer and the protective layer material. A5 shows the edge cleaning process of the metal-based patterning material. A5 specifically shows that the metal-based patterning material located at the edge of the wafer is washed away, and the EPL material (dark gray part) at the edge of the wafer is exposed. A6 shows the exposure process of the metal-based patterning material left on the wafer. After selective exposure with a mask, the exposed area and the unexposed area of the metal-based patterning material have structural differences, so that their solubility to the developer is different. After developing with the developer, a metal-based patterning film is left on the surface of the wafer (as shown in A7). Finally, the aforementioned EPL material is removed by using a specific solvent.

[0047] In theory, an EPL material used to reduce metal contamination should not be significantly soluble in the solvent of the metal-based patterning composition, in the edge bead remover used in the edge bead removal process of the metal-based patterning material, in the developer used in the developing process, and should be easily removed after the developing of the metal-based patterned film without damaging the pattern of the patterned film. However, few EPL materials used in the field can 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 contamination. For example, as the requirement for the feature size of the pattern in the electronic device manufacturing process is continuously reduced, the thickness of the EPL material should be close to the coating thickness of the metal-based patterning material, and the thickness of the EPL material is getting smaller and smaller, which requires that the EPL material with a relatively thin thickness should still not be significantly soluble in the solvent, developer and edge bead remover of the metal-based patterning material, otherwise the ability of anti-metal contamination will be greatly reduced. In view of this, the present application provides a protective layer composition which can effectively reduce the metal contamination of the non-patterned area in the electronic device manufacturing process and the application thereof.

[0048] The protective layer composition for reducing the metal contamination of the edge of the substrate provided by the embodiments of the present application comprises a polyetherimide and an organic solvent, the polyetherimide comprises etherimide repeating units derived from a diamine and an aromatic diether anhydride; and the content of metal ions in the protective layer composition is less than or equal to 10 ppb.

[0049] The polyetherimide with etherimide repeating units in the protective layer composition has no obvious solubility in the solvent, edge bead remover and developer of the metal-based patterning composition, especially has excellent corrosion resistance in ketones, esters and acidic solutions, so the protective layer composition can be arranged at the edge of the substrate, and the protective layer material formed thereby can stably exist at the edge of the substrate during the coating and developing of the metal-based patterning composition. Even if the metal ions in the metal-based patterning composition flow to the side and back of the substrate during the coating and developing, the presence of the protective layer material at the edge of the substrate can ensure 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 yield of the electronic device prepared is high and the performance is stable. Similarly, the protective layer composition can also reduce the metal contamination caused by the supporting layer material of the metal-based patterning composition.

[0050] In addition, the polyetherimide prepared by the reaction of a diamine and an aromatic diether anhydride generally contains ppm level of metal ions (the metal ions generally originate from the raw materials such as the diamine and the diether anhydride, or the ambient atmosphere during the synthesis of the polyetherimide), while the metal ion content of the protective layer composition containing the polyetherimide is controlled to be less than or equal to 10 ppb in the present application, so that the protective layer composition can be practically used for the edge protection of the substrate against metal contamination.

[0051] In the present application, the polyetherimide has the following characteristic peaks in the infrared spectrum: a carbonyl (-C(=O)) stretching vibration peak at 1779 cm -1 , 1722 cm -1 , a carbonyl bending vibration peak at 720 cm -1 , a C-N-C stretching vibration characteristic peak in the imide ring at 1604 cm -1 , a C-N stretching vibration peak at 1340 cm -1 , and characteristic absorption peaks of ether bonds (-O-) at 1225 cm -1 and 1097 cm -1 .

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

[0053]

[0054] wherein T is -O- or -O-Z-O-, Z is independently selected at each occurrence from a divalent group containing at least one aromatic ring, and R is independently selected at each occurrence from one or more of C 2-20 divalent hydrocarbon groups with or without heteroatoms.

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

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

[0057] In the present application, the main chain of the above-mentioned etherimide repeating unit contains at least one ether oxygen bond (-O-). When T is -O-, the main chain of the above-mentioned etherimide repeating unit contains one ether oxygen bond (-O-); when T is -O-Z-O-, the main chain of the above-mentioned etherimide repeating unit contains at least two ether oxygen bonds. The etherimide repeating unit represented by formula (I) can ensure that the above-mentioned polyetherimide has good resistance to solvents, edge trimmers, and developers (such as aliphatic ketones, aliphatic alcohols, ester solvents, etc.) commonly used in metal-based patterning compositions, and thus the protective layer material containing the polyetherimide has a very low degree of dissolution in the coating, edge trimming, and developing processes of the metal-based patterning composition, which can effectively reduce the pollution of the metal to the substrate.

[0058] In formula (I), the bonding position of T can be at the 3,3', 4,4', 3,4', or 4,3' positions 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 ether oxygen atoms, so it is called a divalent group. Among them, Z can be a divalent aromatic group (i.e., an arylene group) with or without heteroatoms, and the number of carbon atoms thereof can be 6-24. The divalent aromatic group with or without heteroatoms can be monocyclic or polycyclic. Among them, the monocyclic divalent aromatic group can be a substituted or unsubstituted phenylene group. The polycyclic divalent aromatic group with or without heteroatoms can be a fused ring or a non-fused ring; among them, the non-fused 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)-, a C 1-18 divalent hydrocarbon group, etc.; each aromatic ring can have or not have a substituent.

[0061] In some embodiments of the present application, Z is selected from the structures represented by formula (1):

[0062]

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

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

[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 substituents on each phenylene group; when a = 0, it represents no substituent on the left benzene ring in formula (1), and when b = 0, it represents no substituent on the right benzene ring in formula (1). When a and b are non-zero integers, they can specifically 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 represented by formula (1) is a non-fused polycyclic divalent aromatic group, and the 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 , a halogen atom can be selected from one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). An unsubstituted alkyl group or an unsubstituted alkoxy group can be linear or branched. An alkoxy group can be understood as an alkyl group containing an ether bond (-O-) connecting group. Among them, the substituents in the substituted alkyl group and the substituted alkoxy group can include halogen atoms, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, etc. In some embodiments, the substituted alkyl group can be a halogenated alkyl group, which can specifically be a perhalogenated alkyl group or a partially halogenated alkyl group. Similarly, the substituted alkoxy group can be a halogenated alkoxy group.

[0070] , a halogen atom can be selected from one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). An unsubstituted alkyl group or an unsubstituted alkoxy group can be linear or branched. An alkoxy group can be understood as an alkyl group containing an ether bond (-O-) connecting group. Among them, the substituents in the substituted alkyl group and the substituted alkoxy group can include halogen atoms, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, etc. In some embodiments, the substituted alkyl group can be a halogenated alkyl group, which can specifically be a perhalogenated alkyl group or a partially halogenated alkyl group. Similarly, the substituted alkoxy group can be a halogenated alkoxy group.

[0071] In some embodiments of the present application, X is C with or without heteroatoms 1-18 A divalent hydrocarbon group. Wherein, "divalent hydrocarbon group" refers to a group formed by removing two hydrogen atoms bonded to carbon atoms in a hydrocarbon; can be saturated or unsaturated; can be linear, branched or cyclic. Specifically, the divalent hydrocarbon group can include one or more of linear or branched alkylene, cycloalkylene, chain or cyclic alkenylene, chain or cyclic alkynylene, arylene; these divalent hydrocarbon groups can be unsubstituted or substituted; can contain heteroatoms or not. Wherein, "heteroatom" refers to an atom other than carbon and hydrogen, for example, can be one or more of oxygen atom (O), sulfur atom (S), nitrogen atom (N), phosphorus atom (P), boron atom (B), silicon atom (Si), halogen atom (such as F, Cl, Br, I) and the like. Wherein, the number of carbon atoms in alkylene with or without heteroatoms can be 1-18; the number of carbon atoms in cycloalkylene with or without heteroatoms can be 2-18, preferably 3-18; the number of carbon atoms in chain alkenylene, chain alkynylene with or without heteroatoms can be 2-18; the number of carbon atoms in cyclic alkenylene, cyclic alkynylene with or without heteroatoms can be 3-18; the number of carbon atoms in arylene 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 can be replaced by one or more heteroatoms or heteroatom-containing groups, and / or at least some of the carbon atoms in the divalent hydrocarbon group can be replaced by one or more heteroatoms or heteroatom-containing groups. Wherein, the hydrogen atoms in the divalent hydrocarbon group can be replaced by halogen atoms, and 1-valent heteroatom-containing polar groups 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 group (-SO3H) and the like; and / or, at least some of the carbon atoms in the divalent hydrocarbon group are inserted with 2-valent heteroatom-containing linking groups. Exemplarily, the heteroatom-containing linking group can be ether bond (-O-), sulfide bond (-S-), carbonyl (-C(=O)-), -C(=O)-O-, sulfonyl bond (-S(=O)2-), sulfinyl bond (-S(=O)-), substituted or unsubstituted imino (such as -NH-, -N(CH3)-), amide bond (-NHCO-) and the like. Thus, the aforementioned divalent hydrocarbon group with or without heteroatoms can be a substituted or unsubstituted divalent hydrocarbon group with or without the aforementioned heteroatom-containing linking group.

[0073] In some embodiments of the present application, a = 0, b = 0, c = 1. At this time, Z is specifically a structure represented by formula (1a):

[0074]

[0075] Where 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 shown in formula (Ⅰ-a) is relatively easy to synthesize, and the polyetherimide containing this etherimide repeating unit has high solubility in aromatic ethers (such as anisole) and good chemical resistance in fatty ketones, fatty alcohols, alkyl ester solvents, etc. Among them, the substituted or unsubstituted C 1-5 The alkylene group can be 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 replaced C 1-5 Substituents in alkylene groups include one or more of halogen atoms, alkoxy groups, and aryl groups. For example, substituted C... 1-5 The alkylene group is -C(CF3)2- or -C(Ph)2-. Ph represents phenyl. In some embodiments, Z shown in formula (1a) is specifically 2,2-(4-phenylene)isopropylidene.

[0077]

[0078] In the aforementioned formula (I), R originates from the diamine NH2-R-NH2. Each occurrence of R is independently selected from C, which may or may not contain heteroatoms. 2-20 Divalent hydrocarbon group. In some embodiments of this application, R may be selected from straight-chain or branched C groups, with or without heteroatoms. 2-20 Alkylene, with or without heteroatoms C 3-20 Cycloalkylene, with or without heteroatoms C 6-20 One or more of the arylene groups. Specifically, the alkylene group has 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19 carbon atoms. The cycloalkylene group has 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19 carbon atoms, and more specifically, 3-12 or 3-8 carbon atoms. The arylene group has 6-18 or 6-12 carbon atoms. For the distribution and position of heteroatoms in the alkylene, cycloalkylene, and arylene divalent hydrocarbon groups, please refer to the preceding description of this application; that is, at least some hydrogen atoms and / or carbon atoms in these hydrocarbon groups can be substituted by one or more heteroatoms or heteroatom-containing groups.

[0079] In some embodiments of the present application, R is independently selected at each occurrence from one or more of substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted heterocycloalkylene, substituted or unsubstituted arylene, and substituted or unsubstituted heteroarylene, wherein the substituted alkylene, substituted cycloalkylene, substituted heteroalkylene, substituted heterocycloalkylene, substituted arylene, and substituted heteroarylene can include one or more of halogen atoms, substituted or unsubstituted C 5 In some embodiments of the present application, R is independently selected at each occurrence from one or more of substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted heterocycloalkylene, substituted or unsubstituted arylene, and substituted or unsubstituted heteroarylene, wherein the substituted alkylene, substituted cycloalkylene, substituted heteroalkylene, substituted heterocycloalkylene, substituted arylene, and substituted heteroarylene can include one or more of halogen atoms, substituted or unsubstituted C 5 In some embodiments of the present application, R is independently selected at each occurrence from one or more of substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted heterocycloalkylene, substituted or unsubstituted arylene, and substituted or unsubstituted heteroarylene, wherein the substituted alkylene, substituted cycloalkylene, substituted heteroalkylene, substituted heterocycloalkylene, substituted arylene, and substituted heteroarylene can include one or more of halogen atoms, substituted or unsubstituted C 1-6 In some embodiments of the present application, R is independently selected at each occurrence from one or more of substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted heterocycloalkylene, substituted or unsubstituted arylene, and substituted or unsubstituted heteroarylene, wherein the substituted alkylene, substituted cycloalkylene, substituted heteroalkylene, substituted heterocycloalkylene, substituted arylene, and substituted heteroarylene can include one or more of halogen atoms, substituted or unsubstituted C

[0080] For example, R is -(CH2) 2～20 , -(CH2) m , -(CH2) n , -(CH2) m , -(CH2) n , -(CH2) m , -(CH2) n , -(CH2) m , -(CH2) n , -(CH2) m , -(CH2) n , -(CH2) p , -(CH2) m , -(CH2) n , -(CH2) p , -(CH2) For example, m, n, and p are independently selected at each occurrence from an integer from 1 to 6.

[0081] In some embodiments of the present application, R in formula (I) is selected from C 6-20 In some embodiments of the present application, R in formula (I) is selected from C 6-20 In some embodiments of the present application, R in formula (I) is selected from C

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

[0083]

[0084] wherein d, e are independently selected from an integer from 0 to 4, f is 0 or 1; each occurrence of L1, L2is independently selected from a single bond or C 1-6 alkylene; R 3 , R 4 each occurrence is independently selected from a halogen atom, a substituted or unsubstituted C 1-10 alkyl group, a substituted or unsubstituted C 1-10 alkoxy group; each occurrence of Q is independently selected from a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, a substituted or unsubstituted C 1-5 alkylene group; the position marked with * is the connecting position.

[0085] wherein L1, L2are selected from C 1-6 alkylene, specifically can be methylene (-CH2-), ethylene (-CH2CH2-), n-propylene (-CH2CH2CH2-), n-butylene (-CH2CH2CH2CH2-), n-pentylene (-(CH2)5-), n-hexylene (-(CH2)6-), etc.

[0086] As to R 3 , R 4 , please refer to the description of R 1 , R 2 in formula (1) in the foregoing of the present application. In some embodiments, R 3 , R 4 are independently selected from a halogen atom, a halogenated or unhalogenated C 1-6 alkyl group, a halogenated or unhalogenated C 1-6 alkoxy group, further selected from a halogen atom, a halogenated or unhalogenated C 1-4 alkyl group, a halogenated or unhalogenated C 1-4 alkoxy group. When d, e are non-zero integers, specifically can be 1, 2, 3 or 4.

[0087] In some embodiments, in formula (2), L1, L2are both single bonds, f = 1, and thus formula (2) is specifically: In some other embodiments, f = 0, and thus formula (2) is specifically: Further, f = 0 and L1, L2are both single bonds, and thus 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, e is an integer from 0 to 4, L1, L2are independently selected from a single bond or C 1-6 alkylene; R 3 , R 4 are independently selected from a halogen atom, C 1-4 alkyl, C 1-4 alkoxy; Q is selected from a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, C 1-5 alkylene.

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

[0091]

[0092] Q in formula (2h) is defined as above in formula (2). Wherein, if Q is a halogenated or unhalogenated C 1-5 alkylene, which can be specifically -(CH2) 1～5 -, -C(CH3)2-, etc.

[0093] When R in formula (I) is selected from the structures shown in formulae (2a) to (2l), the corresponding diamine NH2-R-NH2is easier to obtain, the reactivity of the diamine in the reaction with aromatic diether anhydride to form polyetherimide is higher, and the solubility of the polyetherimide having the repeating unit of formula (I) in aromatic solvents such as anisole is higher.

[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 units (which can be referred to as etherimide repeating units A) in which R is selected from the structures shown in formulae (2a) to (2l) is above 50%. This helps to ensure that the aforementioned polyetherimide has a higher solubility in aromatic solvents such as anisole, and has better corrosion resistance to common metal-based patterning composition solvents, edge trimmers, and developers (such as aliphatic ketone, aliphatic alcohol, and alkyl ester solvents). Further, when R in formula (I) is selected from the structures shown in formulae (2a) to (2l), Z is 2,2-(4-phenylene)isopropylidene.

[0095] In some embodiments of the present application, the polyetherimide further comprises imide repeat units derived from a diamine and an aromatic dianhydride. The main chain of the imide repeat units does not contain ether oxygen bonds (-O-). The introduction of repeat units of other structures can adjust the solubility of the polyetherimide in different solvents. Among them, the molar fraction of the above imide repeat units in all repeat units of the polyetherimide can be 0-10%, further can be 0-5%, or 0-2%, etc. Exemplarily, the molar fraction of the imide repeat units can be specifically 0.1%, 0.2%, 0.5%, 1%, 1.5%, 2%, 3%, 4%, 4.5%, 5%, etc.

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

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

[0098] In some embodiments of the present application, the imide repeat units can include one or more of the structures represented by formula (II), formula (III), formula (IV):

[0099]

[0100]

[0101] wherein R is independently selected at each occurrence from one or more of an alkylene group with or without heteroatoms, a cycloalkylene group with or without heteroatoms, an arylene group with or without heteroatoms, and W is different from the aforementioned T. W does not contain ether oxygen bonds (-O).

[0102] wherein W can be independently selected at each occurrence from one or more of a single bond, -S-, -S(=0)2-, -S(=0)-, -C(=0)-, halogenated or unhalogenated alkylene, halogenated or unhalogenated arylene. In some embodiments, W can be halogenated or unhalogenated arylene, or halogenated or unhalogenated arylene having at least one of -S-, -S(=0)2-, -S(=0)-, -C(=0)- in the backbone. In some embodiments, W in formula (II) is -S-, -S(=0)2-, -C(=0)-, -Ph-S-Ph-, or -Ph-C(=0)-Ph-; wherein -Ph- represents phenylene.

[0103] In some embodiments, the aromatic dianhydride can include one or more of the following:

[0104]

[0105] wherein W is defined as above.

[0106] Exemplarily, the aromatic dianhydride of formula (ii) can include one or more of the following:

[0107]

[0108] In some embodiments, the aromatic dianhydride of formula (i) can be synthesized from a diamine and an aromatic dianhydride. In some embodiments, the aromatic dianhydride of formula (i) can be synthesized from an aromatic dianhydride of formula (ii) and a diamine of formula NH2-R-NH2:

[0109] wherein T and R are defined as above.

[0110] Exemplarily, the aromatic dianhydride of formula (i) can include one or more of the following:

[0111]

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

[0113] Exemplary diamines of the general formula NH2-R-NH2 can include one or more of ethylenediamine, 1,2-propanediamine (chemical formula NH2CH2CH(NH2)CH3), trimethylenediamine (chemical formula NH2-(CH2)3-NH2, also known as 1,3- propanediamine), 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-methylnonamethylenediamine (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 (chemical formula NH2- (CH2)3-CH(OCH3)-(CH2)3-NH2), 2,2-dimethylpropylenediamine (chemical formula NH2-CH2-C(CH3)2-CH2-NH2), diethylenetriamine (chemical formula as shown in Formula (A)), triethylenetetramine (chemical formula as shown in Formula (B)), N- methyl-bis(3-aminopropyl)amine (chemical formula as shown in Formula (C)), 1,2- bis(3-aminopropoxy)ethane (chemical formula as shown in Formula (D)), bis(3- aminopropyl) sulfide (chemical formula NH2-(CH2)3-S-(CH2)3-NH2), 1,4- cyclohexanediamine, bis-(4-aminocyclohexyl) methane (chemical formula as shown in Formula (E)), m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,6- diaminotoluene, m-xylylenediamine, p-xylylenediamine, 2-methyl-4,6-diethyl-l,3- phenylene-diamine (chemical formula as shown in Formula (F)), 5-methyl-4,6-diethyl- 1,3-phenylene-diamine (chemical formula as shown in Formula (G)), benzidine, 3,3'- dimethylbenzidine (chemical formula as shown in Formula (H)), 3,3'-dimethoxybenzidine (chemical formula as shown in Formula (I’)), 1,5-diaminonaphthalene, bis(4- aminophenyl) methane (chemical formula as shown in Formula (J)), bis(2-chloro-4- amino-3,5-diethylphenyl) methane (chemical formula as shown in Formula (K)), 2,2-bis(4-aminophenyl)propane (formula as shown in formula (L)), 1,3-diamino-4- isopropylbenzene (formula as shown in formula (M)), bis(4-aminophenyl)ether (formula as shown in formula (N)), bis(4-aminophenyl)sulfide (formula as shown in formula (O)), bis-(4-aminophenyl)sulfone (formula as shown in formula (P), also known as sulfonamidophenylamine). In some embodiments, the organic diamine includes one or more of m-phenylenediamine, p-phenylenediamine, 2,2-bis(4-aminophenyl)propane, sulfonamidophenylamine.

[0114]

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

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

[0117] (2) the reaction solution is coated on a substrate and baked to form a film, and then the imidization of the film is completed by heat treatment, and the polyetherimide film is peeled off from the substrate.

[0118] In step (1), the protective atmosphere can be nitrogen or the like. The aprotic solvent can include N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), dimethyl sulfoxide (DMSO), etc. The reaction solution includes a polyamide acid with an ether oxygen bond in the main chain (i.e., polyetheramide acid).

[0119] In step (2), the substrate can be a clean glass substrate or the like. The baking can be performed at a temperature of 50°C-120°C (for example, specifically 60°C, 70°C, 80°C, 90°C, etc.) in a vacuum environment. The baking time can be 0.5h-12h, for example, specifically 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 polyetheramide acid dry film, and can reduce the temperature and time of the subsequent imidization reaction.

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

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

[0122] In some embodiments of the present application, the reaction raw material for synthesizing the polyetherimide described above further includes aromatic dianhydride without ether oxygen bond in the main chain. In this way, the polyetherimide has repeating units derived from the aromatic dianhydride and diamine NH2-R-NH2.

[0123] In the present application, the polyetherimide used in the protective layer composition described above can have a low level of residual volatile species. The residual volatile species can be derived from one or more of residual solvent, residual reaction raw material (such as excess diamine or dianhydride), water, or the like. In some embodiments, the polyetherimide has a concentration of residual volatile species less than 1000 ppm, further less than 500 ppm, preferably less than 300 ppm, even less than 100 ppm, or the like. In this way, the residual volatile species in the final polymer product can be reduced to a low level by known methods (such as devolatilization or distillation). The devolatilization or distillation can be performed at normal pressure or under reduced pressure. A suitable devolatilization device can be a wiped film evaporator, a devolatilization extruder, or the like.

[0124] In embodiments of the present application, the polyetherimide has a glass transition temperature (T g ) in the range of 200-280°C. The T g can be obtained from the polymer curve measured by differential scanning calorimetry (i.e., DSC method). g The T

[0125] In some embodiments of the application, the polyetherimide produced can be heated to a molten state and filtered to remove foreign matter, carbonized particles, crosslinked resin, or the like. The melt filtration can be performed after the polyetherimide material is synthesized or later (e.g., prior to using the polyetherimide to formulate the protective layer composition described above). The polyetherimide can be melt filtered during an extrusion operation. The melt filtration can be performed using a filter having a pore size sufficient to remove particles having a size of 40 microns or greater. Further, the filter used for the melt filtration can have a pore size sufficient to remove particles having a size of 100 microns or greater.

[0126] In embodiments of the application, the polyetherimide has a melt index of 0.1 to 10 g / min at 340°C to 370°C. The melt index can be measured according to American Society for Testing Materials (ASTM) D1238. The test instrument is a melt indexer. The melt index test method generally involves melting the polymer material into a melt and then measuring the mass of the polymer melt that passes through a standard die capillary (e.g., a 0.0635 inch diameter capillary) at a specified temperature (e.g., 340°C to 370°C) and pressure over a specified time period (typically 10 minutes). The higher the melt index value, the lower the viscosity and molecular weight of the polymer, and the better the processability; conversely, the lower the melt index value, the higher the viscosity and molecular weight of the polymer, and the worse the processability.

[0127] The polyetherimide described above having a suitable melt index can reflect that it has a suitable relative molecular weight, and accordingly the protective layer material containing the polyetherimide described above can be controlled to have a chemical etching rate in different solvents. Illustratively, the melt index of the polyetherimide can be specifically 0.2 g / min, 0.5 g / min, 1.0 g / min, 2.0 g / min, 1.0 g / min, 2.0 g / min, 3.0 g / min, 4.0 g / min, 5.0 g / min, 6.0 g / min, 7.0 g / min, 8.0 g / min, 9.0 g / min, etc.

[0128] In some embodiments, the polyetherimide has an intrinsic viscosity greater than 0.2 dL / g, such as 0.35 to 0.7 dL / g, in m-cresol at 25 °C. The intrinsic viscosity, which can also be referred to as the "limiting viscosity number", is the specific viscosity of a polymer solution as the concentration of the solution approaches zero, and does not change with the concentration of the polymer solution. The intrinsic viscosity can be measured by using an Ubbelohde viscometer or a capillary viscometer at 25 °C for a polyetherimide in m-cresol. At a given temperature and solvent, the limiting viscosity number of a given polymer is only related to its relative molecular weight. Exemplary intrinsic viscosities can be 0.4 dL / g, 0.45 dL / g, 0.5 dL / g, 0.55 dL / g, 0.6 dL / g, 0.65 dL / g, etc.

[0129] In some embodiments, the polyetherimide has a weight average molecular weight Mw w In the range of 1000 to 150000. The Mw w The Mw of the polyetherimide can be measured by gel permeation chromatography (GPC) using polystyrene as a standard. The Mw of the polyetherimide can be measured by gel permeation chromatography (GPC) using polystyrene as a standard. w In a suitable range, the polyetherimide can have a Mw that is suitable to ensure that a protective layer containing the polyetherimide has good resistance to dissolution in aliphatic solvents, and can be quickly dissolved by aromatic solvents. Exemplary Mw of the polyetherimide can be in the range of 5000 to 80000. w In some embodiments, the Mw of the polyetherimide can be 2000, 5000, 6000, 7000, 8000, 10000, 11000, 12000, 15000, 18000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, 60000, 70000, 80000, 90000, 100000, 120000, 140000, etc. w In some embodiments, the Mw of the polyetherimide can be in the range of 5000 to 80000.

[0130] In some embodiments, the polyetherimide includes a first polyetherimide and a second polyetherimide, wherein the first polyetherimide has a weight average molecular weight less than the weight average molecular weight of the second polyetherimide. The first polyetherimide and the second polyetherimide can have the same or different repeating units. Further, the first polyetherimide has a weight average molecular weight Mw w In some embodiments, the Mw of the first polyetherimide can be in the range of 1000 to 10000, and the Mw of the second polyetherimide can be in the range of 10000 to 150000. wIn the range of greater than 10,000 to less than or equal to 150,000. In this way, in the synergistic cooperation of the low molecular weight polyetherimide and the high molecular weight polyetherimide, the protective layer material containing them is more advantageous in that the thickness of the protective layer material containing them does not substantially change significantly (e.g., does not substantially increase or decrease in thickness) after being soaked in a fatty ketone solvent, a fatty alcohol solvent, an ester solvent, or an acidic solution thereof, is better resistant to corrosion of these solvents, and ensures that the protective layer material containing them is not removed for too long and is easier to remove when removed by a solvent such as anisole. In some embodiments, the Mw of the first polyetherimide is greater than 10,000 and less than or equal to 15,000, further can be greater than 12,000 and less than or equal to 15,000, greater than 13,000 and less than or equal to 15,000, greater than 14,000 and less than or equal to 15,000, etc. w 5000-10000, further can be 6000-9500, 8000-10000, 8000-9500, etc. The Mw of the second polyetherimide can be greater than 10,000 and less than or equal to 15,000, further can be greater than 12,000 and less than or equal to 15,000, greater than 13,000 and less than or equal to 15,000, greater than 14,000 and less than or equal to 15,000, etc. w 1-8, for example, can be 1.2-5, 1.5-3, etc.

[0131] 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 soaked in cyclohexanone is greater than and less than The thickness loss rate of the first film soaked in methyl isobutyl carbinol is less than The thickness loss rate of the first film soaked in anisole is greater than At 25°C, the thickness loss rate of the second film soaked in cyclohexanone is less than The thickness loss rate of the second film soaked in methyl isobutyl carbinol is less than The thickness loss rate of the second film soaked in anisole is greater than

[0132] Controlling the solubility of the film of the low molecular weight first polyetherimide and the film of the high molecular weight second polyetherimide in different solvents to meet the above requirements can better ensure that the dry film of the above protective layer composition containing both the first polyetherimide and the second polyetherimide is better resistant 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 soaked in cyclohexanone for 60s is greater than and less than The thickness loss of the first film soaked in methyl isobutyl carbinol for 60s is less than The thickness loss of the first film soaked in anisole for 10s is greater than At 25°C, the thickness loss of the second film soaked in cyclohexanone for 60s is less than The thickness loss of the second film soaked in methyl isobutyl carbinol for 60s is less than The thickness loss after soaking in anisole for 10 seconds is greater than

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

[0134] In some embodiments of the present application, the mass ratio of the second polyetherimide to the first polyetherimide in the protective layer composition is greater than or equal to 1, for example, the mass ratio is 1-20. This is more conducive to the protective layer composition being resistant to the corrosion of fatty ketone solvents, fatty alcohol solvents, etc., and ensures that the protective layer material containing them is not too long in removal time 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 embodiments of the present application, the total mass percentage content of polyetherimide in the protective layer composition is 0.1wt%-20wt%. The mass percentage content of polyetherimide in the protective layer composition can be adjusted according to the desired thickness of the protective layer film, and generally the higher the solution concentration, the thicker the film layer obtained. For example, the mass percentage content of polyetherimide can be specifically 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 content of polyetherimide is more than 3wt%. In some other embodiments, the mass percentage content of polyetherimide is less than 15wt%. In some embodiments, the mass percentage content of polyetherimide is 1wt%-10wt%. In this case, the protective layer composition is not prone to excessive flow, and the thickness of the film formed by coating is relatively low, so as to better match the patterned process with small pattern feature sizes.

[0136] In some embodiments of the present application, the organic solvent used in the protective layer composition can include one or more of anisole, gamma butyrolactone, N-methyl-2-pyrrolidone, aromatic hydrocarbon. Further, the organic solvent can also include one or more of cyclohexanone, cyclopentanone, dialkyl ketone (alkyl group having 1-6 carbon atoms), alkyl acetate (alkyl group having 1-6 carbon atoms). In the case where the organic solvent includes at least one of the above-mentioned anisole, gamma butyrolactone (GBL), N-methyl-2-pyrrolidone, aromatic hydrocarbon, a suitable amount of aliphatic solvent can be further included. Exemplary dialkyl ketone can include, but is not limited to, one or more of methyl ethyl ketone, ethyl isopropyl ketone, 2-hexanone, methyl isobutyl ketone, methyl isopropyl ketone, 3-methyl-2-pentanone, 2-pentanone, 3-pentanone, and the like. Exemplary alkyl acetate can include, but is not limited to, one or more of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, and the like. Exemplary aromatic hydrocarbon solvent can include one or more of benzene, toluene, xylene, and the like.

[0137] In some embodiments of the present application, the protective layer composition can further include an additive. The additive can include, but is not limited to, one or more of ultraviolet absorber, stabilizer, lubricant, plasticizer, pigment, dye, colorant, antistatic agent, metal deactivator, release agent, and the like. These additives can be added as needed. The additive can be included in an amount of 3 wt% or less, for example, in an amount of 0.01-3 wt%, and further in an amount of 0.01-1 wt% based on the total weight of the protective layer composition.

[0138] The stabilizer can include one or more of light stabilizer (e.g., ultraviolet stabilizer), voltage stabilizer. Exemplary stabilizer can include one or more of phosphorus-containing stabilizer, hindered phenol stabilizer, and the like. The phosphorus-containing stabilizer can include, but is not limited to, phosphite (e.g., triaryl phosphite), phosphonate (e.g., aryl phosphate), and the like. In order to reduce the loss of the stabilizer, the relative molecular weight of the phosphorus-containing stabilizer can be in the range of 300-5000, and the relative molecular weight of the hindered phenol stabilizer can be 500 or more.

[0139] Generally, the polyetherimide prepared by reacting a diamine and a diether anhydride material contains ppm level of metal ions, and the metal ion content in the protective layer composition obtained by directly mixing the polyetherimide with an organic solvent or the like is also in ppm level or even higher. In the present application, the metal ion content in the protective layer composition is controlled to be less than or equal to 10 ppb. In this way, the protective layer composition can be used for the edge of a substrate to prevent metal contamination. The metal ion content in the protective layer composition can be reduced before the protective layer composition is applied to the edge of the substrate. For example, the protective layer composition can be subjected to ion exchange treatment to reduce the metal ion content, and / or the metal ion content can be reduced by extraction in an acidic solution. For example, the metal ion content in the protective layer composition can be specifically 10 ppb, 9 ppb, 8 ppb, 7 ppb, 6 ppb, 5 ppb, 4 ppb, 3 ppb, 2 ppb, 1 ppb, etc. In some embodiments of the present application, the metal ion content in the protective layer composition is less than or equal to 5 ppb, and further less than or equal to 4 ppb.

[0140] The present application also provides a use of the protective layer composition described above for reducing metal contamination in a non-patterned region in a patterning process.

[0141] Specifically, the use is for reducing metal contamination of a metal-based patterning material or a supporting layer material thereof in a non-patterned region. The "non-patterned region" refers to a non-intended region where the metal-based patterning material or the supporting layer material thereof is not intended to be disposed, such as the edge of a substrate, or the edge of an electronic device.

[0142] Correspondingly, the present application also provides a use of a polyetherimide for reducing metal contamination in a non-patterned region in a patterning process, wherein the polyetherimide comprises etherimide repeating units derived from a diamine and an aromatic diether anhydride.

[0143] The protective layer composition described above containing the polyetherimide, or the polyetherimide described above can be disposed at the edge of a substrate to serve as an edge protection material, and in a semiconductor patterning process, the metal-based patterning material or the supporting layer material thereof can be prevented from flowing to the edge of the substrate to directly contact the edge of the substrate, thereby achieving the effect of preventing metal contamination. In this way, a high-quality patterned film can be formed on the substrate, and at the same time, metal contamination of the non-patterned region of the electronic device substrate can be prevented, thereby improving the yield and performance reliability of the electronic device. The specific structure / physical and chemical properties of the polyetherimide can be found in the foregoing description of the present application.

[0144] The present application also provides a method for manufacturing an electronic device, comprising:

[0145] S01, applying the protective layer composition described above of the present application to the edge of a substrate to form a protective layer;

[0146] Step S02, coating a metal-based patterning composition on one side surface of the substrate to form a metal-based patterning material film layer on the substrate and the protective layer;

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

[0148] Step S04, sequentially exposing and developing the metal-based patterning material film layer left on the substrate to form a metal-based patterning thin film on the substrate;

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

[0150] In step S01, the substrate can be selected according to specific needs, for example, it can be a silicon wafer (such as shown in FIG. A1), and the surface of the silicon wafer can or can not have other coatings. The other coatings can be one or more of an anti-reflective coating, an epitaxial layer, a metal layer, a dielectric layer, a modification layer, etc. Of course, in other embodiments, the substrate can also be non-circular, for example, a rectangular sheet, etc. Figure 1 In some embodiments of the present application, the protective layer composition is disposed on the peripheral region of one side surface (the surface to be coated with the metal-based patterning material) of the substrate, such as the peripheral region of the upper surface of the substrate shown in FIG. A2 (see the dark gray part). In this case, the edge of the substrate includes the peripheral region of one side surface of the substrate. The peripheral region is also the non-patterning region of the surface of the substrate. The other region surrounded by the peripheral region is the patterning region of the upper surface of the substrate (see the region indicated by the arrow in FIG. A2), which is the ideal reserved region of the patterning material. Only the patterning material is reserved on the patterning region during exposure. In some other embodiments of the present application, the protective layer composition is disposed on the peripheral region of one side surface (such as the upper surface or the front surface) of the substrate and covers the side surface of the substrate. The side surface is adjacent to the upper surface. In this case, the edge of the substrate includes the peripheral region of one side surface of the substrate and the side surface. In some other embodiments of the present application, the protective layer composition is disposed on the peripheral regions of the two side surfaces of the substrate arranged oppositely and covers the side surface of the substrate (such as shown in FIG. A2). The side surface is located between the two side surfaces of the substrate arranged oppositely. For example, the protective layer covers the peripheral region of the upper surface (or the front surface) of the substrate, the peripheral region of the lower surface (or the back surface) of the substrate, and the side surface of the substrate. In this case, the edge of the substrate includes the peripheral regions of the two side surfaces of the substrate arranged oppositely and the side surface.

[0151] Figure 1 Figure 1

[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 embodiments, the protective layer composition is applied at a thickness of 10 nm to 1000 nm; and / or, the protective layer composition is applied at a width of 0.5 mm to 1.5 mm. In some embodiments, the protective layer composition is applied at a thickness of at least 10 nm, at least 50 nm, at least 100 nm, at least 200 nm, or at least 300 nm. Additionally, the protective film composition is applied at a thickness of at most 900 nm, or at most 800 nm. In some embodiments, the protective layer composition is applied at a width of at least 0.6 mm, at least 0.7 mm, at least 0.75 mm. Additionally, the protective film composition is applied at a width of at most 1.2 mm, at most 1.0 mm. The width of the application of the protective layer composition specifically refers to the width of the application of the protective layer composition to the peripheral region of the side surface of the substrate, and does not include the width of the application of the protective layer composition to the side surface of the substrate. Figure 1 In A2, the width of the dark gray circular ring is specifically indicated.

[0153] In some embodiments, the protective layer composition can be formed without heating after the direct spin coating of the protective layer composition. During the spin coating process, the organic solvent in the protective layer composition is volatilized. Without additional heating after the application of the protective layer composition, the process steps can be simplified, and the protective layer containing a small amount of organic solvent does not affect the etch resistance of the solvent, edge cleaning agent, etc. in the metal-based patterning composition. In some other embodiments, a heating process (as indicated in A3 above) can be performed after the application of the protective layer composition to further remove the residual organic solvent in the protective layer. In some embodiments, the heating process can be performed at a temperature in the range of 150-350 °C (e.g., 180 °C, 200 °C, 220 °C, 250 °C, 280 °C, 300 °C, etc.) for a time period of 30-120 s (e.g., 45 s, 60 s, 90 s, etc.). Figure 1

[0154] In step S02, the metal-based patterning composition refers to a patterning composition containing a metal element. In some embodiments, the metal element-containing patterning composition can be a metal oxide photoresist (MOR), a metal complex-containing photoresist, etc. Metal-based patterning materials can include, but are not limited to, those mentioned in U.S. Patent Nos. 9,315,636; 8,568,958; 9,201,305; 9,296,922; 9,409,793; and 9,499,698; and U.S. Patent Application Nos. 62 / 437,449 (filed on December 21, 2016) and 14 / 978,232 (filed on December 22, 2015), which are incorporated herein in their entirety.

[0155] ​In some embodiments of the present application, the metal-based patterning composition described above can be disposed on the substrate by coating. The specific coating method can be spin coating. When spin coating is used, the solvent used in the metal-based patterning composition should not have a detrimental effect on the protective layer material of the embodiments of the present application. The solvent in the metal-based patterning composition includes, but is not limited to, one or more of fatty ketone solvents, fatty alcohol solvents, ester solvents, etc. Illustratively, the fatty ketone solvent can include one or more of cyclohexanone, 4-methyl-2-pentanone, etc. The fatty alcohol solvent can include one or more of PGME (propylene glycol ethyl ether), methoxyethanol, ethoxypropanol, ethoxyethanol, 1-pentanol, 4-methyl-2-pentanol, methyl isobutyl carbinol, etc. The ester solvent can be PGMEA (propylene glycol methyl ether acetate), ethyl lactate, etc.

[0156] In addition, during the spin coating of the metal-based patterning composition on one side surface of the substrate, it can flow to the non-patterning area of the substrate (such as the peripheral area of the front surface of the substrate, the side surface of the substrate, the back surface of the substrate, etc.) and cover the substrate and the protective layer (such as the protective layer shown in A4) thereon. However, due to the presence of the protective layer, the metal-based patterning composition will not directly contact the non-patterning area of the substrate and cause metal contamination. Figure 1

[0157] In the embodiments of the present application, after the metal-based patterning composition is coated, a baking process can be performed to remove the solvent remaining in the metal-based patterning material film layer. Illustratively, the baking process can be performed at a temperature of 150°C-450°C for 60-120 seconds.

[0158] Step S03 is mainly to remove the metal-based patterning 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 (which can not necessarily be all) of the metal-based patterning material film layer in contact with the protective layer, and in this edge removal process, no detrimental effect should be caused to the metal-based patterning material film layer not in contact with the protective layer. Even after edge removal, some metal-based patterning material in contact with the protective layer material is still retained, as long as the retained portion does not significantly reduce the metal contamination resistance of the protective layer. For example, after edge removal, at most 5% of the metal-based patterning material in contact with the protective film layer can be retained. Figure 1 A5 specifically shows the removal of the metal-based patterning material on the protective layer material at the edge of the wafer.

[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 etching agent can be used to remove at least a portion of the metal-based patterned material film layer in contact with the protective layer. The side etching agent does not have a detrimental effect on the protective layer of the embodiments of the present application. Exemplarily, the side etching 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 etching agent is a mixed solvent of PGMEA and PGME in a volume ratio of 7:3.

[0160] In step S04, the exposure can be a selective exposure, and the exposure source can be used to irradiate the metal-based patterned material film layer left on the substrate through a mask having a predetermined pattern. The exposure source can be a light source having a wavelength of 400 nm or less, X-rays, an electron beam, or the like. After the selective exposure of the metal-based patterned material film layer, the exposed portion undergoes a chemical reaction, which results in a difference in solubility to a developing agent between the exposed portion and the unexposed portion.

[0161] In some embodiments of the present application, a post-exposure bake (PEB) can be performed after the exposure and before the development, to promote the further completion of the chemical reaction in the exposed metal-based patterned material film layer.

[0162] Due to the difference in solubility to the developing agent between the exposed and unexposed portions of the metal-based patterned material film layer, the exposed patterned material film layer can be developed using a developing agent, and a patterned film can be formed on the substrate. After the developing agent treatment, the exposed portion of the patterned material film layer is washed away, and a positive development is obtained, leaving a positive pattern identical to the exposure mask on the substrate. After the developing agent treatment, the exposed portion of the patterned material film layer is not washed away, and a negative development is obtained, leaving a negative pattern complementary to the exposure mask on the substrate.

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

[0164] In step S05, after the removal of the protective layer, the patterned film left on the substrate is spaced apart from the edge of the substrate (as shown in FIG. A8). Figure 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 should have no harmful effect on the patterned film. In some embodiments of the present application, the protective layer can be removed using the organic solvent used to prepare the protective layer composition. For example, one or more of anisole, gamma butyrolactone, N-methyl-2-pyrrolidone, and the like can be used to remove the protective layer. In some embodiments, anisole is used in particular to remove the protective layer. The protective layer is removed at a relatively fast rate and without damaging the metal-based patterned film.

[0166] After 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 serve 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 predetermined pattern on the substrate.

[0167] It can be understood that after step S05, other functional layers can also be formed on the substrate.

[0168] The method for manufacturing an electronic device provided in the embodiments of the present application uses the protective layer composition of the embodiments of the present application to protect the edges of the substrate before the metal-based patterned composition is coated on the substrate. The protective layer composition can stably exist during the formation of the metal-based patterned film (including coating, edge removal, development, and the like), reduces the metal contamination of the metal-based patterned material to the non-patterned regions (such as the edges of the substrate) of the substrate, and can be easily removed after the metal-based patterned film is formed without damaging the patterned film, thereby improving the yield and performance reliability of the electronic device. In addition, when a metal-based patterned film with a small feature size is formed on the substrate, the protective layer has a relatively small thickness, but due to its good corrosion resistance to solvents, edge removal agents, and developers for the metal-based patterned material, it can still effectively play a role in resisting metal contamination.

[0169] The embodiments of the present application also provide an electronic device manufactured using the method for manufacturing an electronic device described above.

[0170] The electronic device can include a semiconductor device (such as a chip), an integrated circuit, and the like. After the preparation of the metal patterned film described above is completed, other functional layers can be prepared. In the final product electronic device, the metal-based patterned film is usually not present.

[0171] The embodiments of the present application are further described below in multiple embodiments.

[0172] Synthesis Example 1

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

[0174] The above reaction solution was slowly cast on a clean glass plate placed horizontally, and a glass rod was used to make it uniformly flat, and then it was placed in a blast oven and baked at 80°C for 10 h to remove most of the DMAc solvent to obtain a pre-baked polyether amic acid film, and then a heating treatment was performed to complete the imidization, and the specific procedure of the heating treatment was: 120°C-1 h, 180°C-1 h, 220°C-1 h. After cooling to room temperature, the polyetherimide was peeled off from the glass plate, denoted as PEI1.

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

[0176]

[0177] The weight average molecular weight M w of the PEI1 was 8432, the M w was 4.58, and the ratio of the M n was 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 w of the PEI2 was 8859, the M w was 4.21, and the ratio of the M n was 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 denoted as PEI3. The weight average molecular weight M w of the PEI3 was 16859, the M w was 8.71, and the ratio of the M n was 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 denoted as PEI4. Among them, the weight average molecular weight Mw of the PEI4 is 6368, Mw / Mn = 2.18, and the number average molecular weight Mn is 2930, as measured by gel permeation chromatography. w w n

[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 denoted as PEI5. Among them, the weight average molecular weight Mw of the PEI5 is 4559, Mw / Mn = 2.53, and the number average molecular weight Mn is 1790, as measured by gel permeation chromatography. w w n

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

[0187]

[0188] Synthesis Comparative Example 1

[0189] Into 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 for 10 minutes at room temperature.

[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 to pH 6-7 with 10 wt% aqueous HCl solution, and then poured into a 1 L flask containing 500 mL of deionized water to form a precipitate. After mixing for 30 minutes, the precipitate was allowed to settle overnight, and then the water (500 mL) was decanted and 1 L of tetrahydrofuran (THF) was added to the remaining sticky solid. The THF solution was immersed in 3 liters of hexane for 1 hour, and then the solid was allowed to settle, and the polymer polysulfone, denoted as PSU1, was precipitated.

[0191] Among them, the reaction formula involved in the synthesis of PSU1 includes: ​​​​​​

[0192]

[0193] wherein the PSU1 has a weight average molecular weight Mwof 16783, Mw / Mn= 2.13, as measured by gel permeation chromatography. w w n

[0194] Synthesis Comparative Example 2

[0195] Synthesis Comparative Example 2 differs from Synthesis Comparative Example 1 in that the reaction time at 150°C is 10 hours. The polysulfone produced in Synthesis Comparative Example 2 is denoted as PSU2.

[0196] wherein the PSU2 has a weight average molecular weight Mwof 54384, Mw / Mn= 1.89, as measured by gel permeation chromatography. w w n

[0197] Different protective layer compositions were prepared according to the formulations shown in Table 1 below. Metal ion impurities (referred to as metal impurities) and particles in the compositions were filtered out using metal ion impurity (metal impurity) filters and particle filters. The filters were connected in series in the following order: (1) an adsorption type metal impurity filter, (2) a chelation type metal impurity filter, (3) an ultra-high molecular weight polyethylene (UPE) particle filter with an average pore size of 10 nm, and (4) a UPE particle filter with an average pore size of 1 nm. The filtration pressure was 0.20 MPa, and the number of cycles was 5-15 times until no particles with a particle size of ≥0.15 μm were detected in the protective layer compositions using a laser particle counter (LPC). The metal ion impurities in the compositions were analyzed using inductively coupled plasma mass spectrometry (ICP-MS). The particles in the compositions were detected using a laser particle counter (LPC).

[0198] Subsequently, each of the filtered protective layer compositions was spin-coated on the edge of a wafer and baked at 250°C for 60 s, and the thickness of the resulting protective layer was measured and summarized in Table 1 below. The wafer with the protective layer was then soaked in a cyclohexanone solvent at 25°C for 60 s, and the wafer was then removed and dried, and the thickness of the remaining protective layer was measured. The results are shown in Table 1.

[0199] Table 1

[0200]

[0201]

[0202] ​​​​​​From Table 1, it can be seen that the protective layer materials of Comparative Examples 1-3 using polysulfone have poor resistance to cyclohexanone solvent, and the film thickness loss ratio after 60s immersion in cyclohexanone is greater than 95%. The protective layer materials of the present application using polyetherimide have much higher resistance to cyclohexanone than Comparative Examples 1-3, under the condition that the polymer content in the protective layer materials is the same.

[0203] In the above Table 1, the protective layer materials of Examples 1-2, 7 and 10 contain one or two of low molecular weight polyetherimides PEI1, PEI2, PEI4 and PEI5. The protective layer material of Example 4 contains high molecular weight polyetherimide PEI3. The protective layer materials of Examples 5-6 contain both high molecular weight polyetherimide PEI3 and low molecular weight polyetherimide PEI2. The protective layer materials of Examples 8-11 contain both high molecular weight polyetherimide PEI3 and low molecular weight polyetherimide PEI4. The protective layer materials of Examples 13-14 contain both high molecular weight polyetherimide PEI3 and low molecular weight polyetherimide PEI5. The protective layer material of Example 12 contains low molecular weight polyetherimide PEI5. The protective layer material of Comparative Example 1 contains polysulfone. The protective layer material of Comparative Example 2 contains polyimide. The protective layer material of Comparative Example 3 contains polyurethane.

[0204] Similarly, the film thickness loss of the protective layer materials of Examples 8-11 containing both high molecular weight PEI3 and low molecular weight PEI4 is also significantly lower than that of Example 7 containing only low molecular weight PEI4. The protective layer materials of Examples 13-14 containing both high molecular weight PEI3 and low molecular weight PEI5 have better resistance to cyclohexanone than the protective layer material of Example 12 containing 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, and the test results are shown in Table 2 below.

[0206] Table 2

[0207]

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

[0209] The following Table 3 shows protective film compositions as representatives, to test the removal effect of the protective layer materials provided by the present application by anisole.

[0210] Specifically, several groups 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 a wafer (e.g. a 200mm wafer) to form a film layer with a thickness of 1-2 microns. Figure 1As shown in Table A2), the wafer was baked at 250°C for 60 seconds to test the coating thickness (i.e., the initial thickness of the protective layer). Then, the wafer was immersed in anisole for 10 seconds, subsequently removed and dried. The remaining protective film thickness was then measured 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] Referring to Tables 1 and 3, it can be seen that the protective layer using both high and low molecular weight PEI in this application can maintain good solvent resistance in cyclohexanone while achieving a relatively fast removal rate in anisole. Furthermore, the protective layer materials of other embodiments in Table 1 can also achieve relatively fast removal in anisole; data for each are not listed here.

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

[0215] Table 4

[0216]

[0217] As shown in Table 4, the protective layer material formed by coating the protective layer composition of Example 13 of this application has good resistance to acidic solutions of 4-methyl-2-pentanone, acidic solutions of cyclohexanone, and methyl isobutyl methanol, regardless of whether baking is performed after coating; and it can be easily removed from anisole solvent.

[0218] To demonstrate that the protective layer material provided in this application embodiment can reduce metal contamination, the following application embodiment 1 is provided.

[0219] Application Example 1

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

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

[0222] (3) As shown in A5, cyclohexanone was used to remove the etch resist material located on the edge of the wafer. Figure 1

[0223] (4) The etch resist layer was exposed using electron beam lithography.

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

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

[0226] (7) The total metal contamination on the backside and side of the wafer was analyzed by ICP-MS technique, in terms of the number of metal atoms per cm2. The test results are summarized in Table 5 below. 2

[0227] According to the method described in Application Example 1, the following application examples were provided, and the metal contamination test results are also summarized in Table 5 below.

[0228] Among them, the difference between Application Example 2 and Application Example 1 is only that the edge of the wafer is coated with the protective layer composition of Example 15.

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

[0230] The difference between Comparative Application Example 2 and Application Example 1 is only that the edge of the wafer is coated with the protective layer composition as in Example 5, but without gold impurity filtration of the protective layer composition, and the total gold impurity test result of this composition is 235 ppb.

[0231] Table 5

[0232]

[0233] From Table 5, it can be known that in Application Examples 1-2, the total metal atom contamination on the backside and side of the wafer was found to be less than 10 10 / cm 2 , meeting the requirements of the semiconductor industry. In Comparative Application Example 1, PSU material was used as the protective material for the edge of the wafer, but because the edge protective material dissolved more in cyclohexanone solvent (see data in Table 1), it did not effectively protect the wafer, resulting in excessive detection of metal ion impurities on the backside and side of the wafer. In Comparative Application Example 2, because the metal element impurities in the protective layer composition used exceeded 10 ppb, metal impurities were left on the edge of the wafer, which also led to excessive detection of metal ion impurities.​​​

[0234] It can be seen that the protective layer composition provided by the embodiments of the present application can have good anti-metal contamination effect, and can reduce the metal contamination caused by the metal-based patterned material and the matching layer material in the unnecessary area of the wafer.

[0235] The above merely expresses the exemplary embodiments of the present application, and the description is relatively specific and detailed, but it should not be understood as limiting the scope of the patent of the present application. It should be noted that, for those skilled in the art, without departing from the concept of the present application, several modifications and improvements can be made, which are all within the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

[0236] It should be understood that the first, second, and various numerical numbers involved herein are only for the convenience of differentiation in description, and are not used to limit the scope of the present application.

[0237] In the present application, the association relationship of "and / or" describing the associated objects indicates that there can be three kinds of relationships, for example, A and / or B can represent the following three cases: A exists alone, A and B exist together, and B exists alone, wherein A and B can be singular or plural. The character " / " generally represents an "or" relationship between the associated objects before and after it.

[0238] In the description of the present application, unless otherwise specified, "a plurality of" means more than or equal to two. "At least one" means one or more. "At least one of the following" or the like means any combination of these items, including any combination of single item or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can represent a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple.

[0239] In addition, the numerical range represented by "-" in the present application means a range including the minimum value and the maximum value represented by the numbers before and after "-" respectively. In the present application, the expressions related to the range of parameters, such as "greater than or equal to (≥)", "less than or equal to (≤)", "above", "below", all include the number. The numerical values and numerical ranges involved in the embodiments of the present application are approximate values, which may have a certain range of error due to the influence of manufacturing process / testing method, etc., which can be considered negligible by those skilled in the art.

Claims

1. A protective layer composition, characterized in that, The protective layer composition comprises a polyetherimide and an organic solvent, wherein the polyetherimide comprises repeating etherimide units derived from diamines and aromatic diether anhydrides; the polyetherimide comprises 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, and the metal ion content in the protective layer composition is less than or equal to 10 ppb.

2. The protective layer composition as claimed in claim 1, characterized in that, The etherimide repeating unit comprises at least one structure as shown in formula (I): Equation (I) Where T is -O- or -OZO-, Z is selected from a divalent group containing at least one aromatic ring, and R is selected from C with or without heteroatoms. 2-20 Divalent hydrocarbon group.

3. The protective layer composition as claimed in claim 2, characterized in that, The Z includes the structure shown in equation (1): Equation (1) Where a, b, and c are independently selected from integers between 0 and 4, and R 1 R 2 Independently selected from halogen atoms, substituted or unsubstituted C atoms 1-10 Alkyl, substituted or unsubstituted C 1-10 One or more of the alkoxy groups; X is selected from single bonds, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O-), and C with or without heteroatoms. 1-18 One of the divalent hydrocarbon groups; * indicates the linking position.

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

5. The protective layer composition as claimed in claim 2, characterized in that, The R includes the structure shown in equation (2): Equation (2) Where d and e are independently selected from integers from 0 to 4, and 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 atoms. 1-10 Alkyl, substituted or unsubstituted C 1-10 One or more of the alkoxy groups; Q is selected from single bonds, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, substituted or unsubstituted C- groups. 1-5 One of the alkylene groups; * indicates the linking position.

6. The protective layer composition as claimed in claim 1, characterized in that, The molar percentage of the repeating etherimide unit in all repeating units of the polyetherimide is 90%-100%.

7. The protective layer composition as claimed in claim 1, characterized in that, The polyetherimide further includes repeating units of imide derived from diamines and aromatic dianhydrides that do not contain ether oxygen bonds.

8. The protective layer composition as claimed in claim 7, characterized in that, The imide repeating unit independently includes one or more of the structures shown in formula (II), formula (III), and formula (IV): Formula (II) Formula (III) Equation (Ⅳ) Wherein, R is selected from one or more of alkylene groups with or without heteroatoms, cycloalkylene groups with or without heteroatoms, and arylene groups with or without heteroatoms; W does not contain ether oxygen bonds.

9. The protective layer composition according to any one of claims 1-8, characterized in that, The polyetherimide satisfies at least one of the following (a) to (c): (a) The melt index of the polyetherimide measured at 340℃-370℃ is 0.1-10 g / min; (b) The intrinsic viscosity of the polyetherimide m-cresol solution 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 claim 1, 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 the following: At 25°C, the thickness loss rate of the first film immersed in cyclohexanone is greater than 0.083 Å / s and less than 0.83 Å / s, the thickness loss rate immersed in methyl isobutyl methanol is less than 0.17 Å / s, and the thickness loss rate immersed in anisole is greater than 1000 Å / s. At 25°C, the thickness loss rate of the second film immersed in cyclohexanone is less than 0.083 Å / s, the thickness loss rate immersed in methyl isobutyl methanol is less than 0.083 Å / s, and the thickness loss rate immersed in anisole is greater than 500 Å / s.

11. The protective layer composition as claimed in claim 1, characterized in that, In the protective layer composition, the mass ratio of the second polyetherimide to the first polyetherimide is 1-20.

12. The protective layer composition as claimed in claim 1, characterized in that, In the protective layer composition, the polyetherimide has a mass percentage content of 0.1wt%-20wt%.

13. The protective layer composition as claimed in claim 1, characterized in that, The organic solvent includes one or more of anisole, γ-butyrolactone, N-methyl-2-pyrrolidone, and aromatic hydrocarbons.

14. The protective layer composition as claimed in claim 1, characterized in that, The protective layer composition further includes one or more of the following: UV stabilizer, voltage stabilizer, lubricant, plasticizer, colorant, antistatic agent, and metal passivator.

15. The protective layer composition as claimed in claim 1, characterized in that, The protective layer composition also includes one or more of ultraviolet absorbers and release agents.

16. The application of the protective layer composition according to any one of claims 1-15 in reducing metal contamination in non-patterned areas during a patterning process.

17. A method for manufacturing an electronic device, characterized in that, include: The protective layer composition as described in any one of claims 1-15 is applied to the edge of the substrate to form a protective layer; A metal-based patterned material is coated on one side surface of the substrate to form a metal-based patterned material film on the substrate and the protective layer; Remove at least a portion of the metal-based patterned material film that is in contact with the protective layer; The metal-based patterned material film layer left on the substrate is sequentially exposed and developed to form a metal-based patterned thin film on the substrate; After development, the protective layer is removed.

18. The manufacturing method as described in claim 17, characterized in that, 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.

19. An electronic device, characterized in that, It is prepared by the manufacturing method described in any one of claims 17-18.

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