CN113234194B - Copolymer, primer composition, double-layer system and application of double-layer system in double-layer stripping process - Google Patents
Copolymer, primer composition, double-layer system and application of double-layer system in double-layer stripping process Download PDFInfo
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- CN113234194B CN113234194B CN202110725188.6A CN202110725188A CN113234194B CN 113234194 B CN113234194 B CN 113234194B CN 202110725188 A CN202110725188 A CN 202110725188A CN 113234194 B CN113234194 B CN 113234194B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
- C08F222/402—Alkyl substituted imides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J135/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
Abstract
The application provides a copolymer, a primer composition, a two-layer system and application thereof in a two-layer stripping process. Belongs to the technical field of semiconductors. The copolymer is obtained by polymerizing an N-substituted maleimide monomer, a dissolution rate control monomer, an acrylate hydrophobic monomer and a hydroxyethyl acrylate hydrophilic monomer. The copolymer is insoluble in a solvent of a traditional photoresist, can be dissolved in an alkaline solution, is insoluble in water, has higher glass transition temperature, better chemical stability and etching resistance, and can be used as a bottom resin material of a double-layer stripping process. The bilayer system includes a top layer photoresist and a copolymer formed underlayer photoresist. The bilayer system can be used for a bilayer stripping process, and a target photoetching pattern can be obtained only by single development and single development, so that the photoetching efficiency is greatly improved.
Description
Technical Field
The application relates to the technical field of semiconductors, in particular to a copolymer, a primer composition, a double-layer system and application of the double-layer system in a double-layer stripping process.
Background
The Lift-off strip process is a fine metal deposition strip process. In the production of microelectronic mechanical system and integrated circuit, Lift-off stripping process is generally used in high-density multilayer wiring, and because the metal lead steps formed by the stripping process have certain inclination, the method is beneficial to realizing interlayer dielectric planarization and improving circuit density. The Lift-off stripping process comprises a single-layer stripping process and a double-layer stripping process, the double-layer stripping process has obvious advantages in the aspects of resolution, undercut control, process simplification, yield and the like compared with the single-layer stripping process, particularly in the aspects of resolution and process tolerance, the double-layer Lift-off stripping process can achieve 0.1 mu m resolution and is far superior to the single-layer Lift-off stripping process, the tolerance range of the double-layer Lift-off stripping process is larger, and different process requirements can be met.
FIG. 1 is a schematic diagram of a double layer Lift-off strip process. Firstly, coating a layer of even bottom glue (Lift-off resist), baking to remove most of solvent in the bottom glue, and forming a compact film; coating Photoresist (PR) on the Photoresist, exposing, developing, and forming a pattern as shown in the figure due to the fact that the lateral dissolution rate of the bottom layer Photoresist in the developing solution is faster than that of the upper layer Photoresist because of the difference of the dissolution rates of the two layers of Photoresist; then depositing a metal layer, stripping the double-layer glue by using an organic solvent, and obtaining a metal pattern on the substrate area which is not protected by the photoresist.
The morphology mechanism of the double-layer Lift-off stripping process for forming the upper part wide and the lower part narrow is different from that of single-layer Lift-off glue. The key of the double-layer Lift-off process is that the dissolution rates of the bottom layer photoresist and the upper layer photoresist in a developing solution are different, and the lateral dissolution rate of the bottom layer photoresist is faster than that of the upper layer photoresist under the same developing condition, so that an undercut morphology is formed, and the penetration of the developing solution is easy. Therefore, the matrix resin suitable for the bottom glue needs to meet the following requirements: solvents that are not soluble in conventional photoresists, such as propylene glycol methyl ether acetate and the like; soluble in alkaline solutions like phenolic resins; is insoluble in water; the glass transition temperature is higher; the chemical stability and the etching resistance are good; good adhesion on silicon wafers, etc.
The underlying resins for the two-layer Lift-off peel process are constantly being developed and studied. One type of currently commercially available primer resin is poly (dimethylglutarimide) (PMGI), which is prepared by reacting polymethyl methacrylate (PMMA) and ammonia gas in a twin-screw extruder at high temperature and high pressure. The preparation method has high requirements on reaction conditions, needs special equipment and has high cost.
Disclosure of Invention
The application provides a copolymer, a primer composition, a two-layer system and application thereof in a double-layer stripping process, which can be used as a primer resin material in the double-layer stripping process.
The embodiment of the application is realized as follows:
in a first aspect, the present disclosure illustratively provides a copolymer derived from free-radical polymerization of a first monomer, a second monomer, a third monomer, and a fourth monomer.
The chemical formulas of the first monomer, the second monomer, the third monomer and the fourth monomer are shown as follows in sequence:
wherein R is 1 Selected from unsubstituted or substituted C 6-18 Aryl, unsubstituted or substituted C 6-18 A cycloalkyl group.
R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen, hydroxy, halogen, C 1-6 Alkyl or C 1-6 Alkoxy, and R 2 、R 3 、R 4 、R 5 、R 6 At least one of which is a hydroxyl group.
R 7 、R 8 Each independently selected from unsubstituted or substituted C 1-6 An alkyl group.
Substituted C 6-18 Aryl, substituted C 1-6 Alkyl and substituted C 1-6 The substituents of the alkyl are respectively and independently selected from halogen and C 1-4 Alkyl or C 1-4 An alkoxy group.
The weight average molecular weight of the copolymer is 5000-100000 g/mol, the polydispersity is less than or equal to 3.5, and the content of the repeating unit formed by the first monomer in the copolymer is 20-60 wt%, the content of the repeating unit formed by the second monomer is 5-35 wt%, the content of the repeating unit formed by the third monomer is 10-45 wt%, and the content of the repeating unit formed by the fourth monomer is 10-40 wt%.
In the technical scheme, the copolymer is insoluble in a solvent of the traditional photoresist, can be dissolved in an alkaline solution, is insoluble in water, has a high glass transition temperature, has high chemical stability and etching resistance, and can be used as a bottom resin material of a double-layer stripping process.
In a first possible example of the first aspect of the present application, in combination with the first aspect, the above R 1 Selected from phenyl, pyrenyl, 1,2,3, 4-tetrahydro-1-naphthyl, 1,2,3, 4-tetrahydro-2-naphthyl, 1,2,3, 4-tetrahydro-1-methyl-2-naphthyl, 1,2,3, 4-tetrahydro-2-methyl-1-naphthyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-diisopropylphenylPhenyl, 2-chlorophenyl, 2-bromophenyl, cyclohexyl, methylcyclohexyl, adamantyl, methyladamantyl, or quinuclidinyl.
R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from the group consisting of hydrogen, hydroxy, fluoro, chloro, bromo, iodo, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2-dimethyl-1-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-1-hexyl, 3-methyl-1-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, iodine, and mixtures thereof, 3-methyl-2-pentyl, 3-methyl-3-pentyl, 2-dimethyl-1-butyl, 3-dimethyl-2-butyl, 2, 3-dimethyl-1-butyl, 2, 3-dimethyl-2-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy or tert-butoxy.
R 7 、R 8 Each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2-dimethyl-1-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-2-pentyl, n-butyl, isobutyl, tert-butyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-pentyl, 2-hexyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-pentyl, and mixtures thereof, 3-methyl-3-pentyl, 2-dimethyl-1-butyl, 3-dimethyl-2-butyl, 2, 3-dimethyl-1-butyl or 2,3, -dimethyl-2-butyl.
In a second possible example of the first aspect of the present application, in combination with the first aspect, R is as described above 1 Is cyclohexyl, R 2 、R 3 、R 5 And R 6 Are each hydrogen, R 4 Is hydroxy, R 7 And R 8 Are all methyl.
In a third possible example of the first aspect of the present application in combination with the first aspect, the content of the repeating unit formed by the first monomer in the above-mentioned copolymer is 20 to 50 wt%, the content of the repeating unit formed by the second monomer is 10 to 30 wt%, the content of the repeating unit formed by the third monomer is 10 to 40 wt%, and the content of the repeating unit formed by the fourth monomer is 10 to 35 wt%.
Optionally, the copolymer has a content of repeating units derived from the first monomer of 30 to 50 wt%, a content of repeating units derived from the second monomer of 10 to 25 wt%, a content of repeating units derived from the third monomer of 15 to 35 wt%, and a content of repeating units derived from the fourth monomer of 10 to 30 wt%.
In a fourth possible example of the first aspect of the present application in combination with the first aspect, the weight average molecular weight of the above copolymer is 10000 to 100000 g/mol.
Optionally, the weight average molecular weight of the copolymer is 10000-80000 g/mol.
Optionally, the weight average molecular weight of the copolymer is 10000-50000 g/mol.
In a fifth possible example of the first aspect of the present application in combination with the first aspect, the polydispersity index of the above-mentioned copolymer is ≦ 3.
Alternatively, the copolymer has a polydispersity ≦ 2.5.
Alternatively, the copolymer has a polydispersity ≦ 2.
In a second aspect, the present application provides an underfill composition comprising an additive, a solvent, and the copolymer described above.
Optionally, the additive comprises a surfactant and a pigment.
In the technical scheme, the primer composition can be used as a primer in a double-layer stripping process.
In a third aspect, the present application provides a bilayer system comprising a top layer photoresist and a bottom layer photoresist formed from the above-described bottom layer photoresist composition.
In the above technical solution, the bilayer system of the present application can be used for a bilayer lift-off process.
In a first possible example of the third aspect of the present application, in combination with the third aspect, the dissolution rate of the bottom layer photoresist in the alkaline developer is faster than the dissolution rate of the top layer photoresist in the alkaline developer under the same exposure condition and the same development condition.
In a fourth aspect, the present application provides a use of the bilayer system in a bilayer stripping process, exposing and developing the bilayer system.
Optionally, the exposure is a single exposure.
Alternatively, the development is a single development.
Optionally, the post-exposure baking temperature is 150-200 ℃.
Optionally, the post-exposure baking time is 2-5 min.
Optionally, the developer solution used for development comprises tetramethylammonium hydroxide developer solution.
Optionally, the concentration of the tetramethylammonium hydroxide developer is 1.19 wt% to 2.38 wt%.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is a schematic diagram of a double layer lift-off process;
FIG. 2 is a graph of the topography of an underlayer adhesive formed of A1 copolymer and a KMP C5315 UV positive photoresist in example 1 of the present application;
FIG. 3 is a graphical representation of the formation of a commercially available PMGI and KMP C5315 UV positive photoresist from MicroChem.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a detailed description of a copolymer, primer composition, bilayer system and its application in a bilayer stripping process according to embodiments of the present application:
the present application provides a copolymer polymerized from a first monomer, a second monomer, a third monomer, and a fourth monomer.
The chemical formulas of the first monomer, the second monomer, the third monomer and the fourth monomer are shown as follows in sequence:
the copolymer has the following chemical formula:
wherein R is 1 Selected from unsubstituted or substituted C 6-18 Aryl, unsubstituted or substituted C 6-18 A cycloalkyl group.
Alkyl includes straight chain alkyl and branched chain alkyl.
R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen, hydroxy, halogen, C 1-6 Alkyl or C 1-6 Alkoxy, and R 2 、R 3 、R 4 、R 5 、R 6 At least one of which is a hydroxyl group.
R 7 、R 8 Each independently selected from unsubstituted or substituted C 1-6 An alkyl group.
Substituted C 6-18 Aryl, substituted C 1-6 Alkyl and substituted C 1-6 The substituents of the alkyl are respectively and independently selected from halogen and C 1-4 Alkyl or C 1-4 An alkoxy group.
The copolymer has the following characteristics that the first monomer is an N-substituted maleimide monomer, the second monomer is a dissolution rate control monomer, the third monomer is an acrylate hydrophobic monomer, and the fourth monomer is a hydroxyethyl acrylate hydrophilic monomer:
1. the copolymer is insoluble in solvents of traditional photoresists such as anisole, propylene glycol methyl ether acetate, ethyl lactate, 2-heptanone, cyclohexanone and the like, and can be obviously layered with the top photoresist when being used as the bottom photoresist of a double-layer stripping process; 2. is insoluble in water and can not be lost when being washed by water after development; 3. soluble in commonly used alkaline developers, such as tetramethylammonium hydroxide developer; 4. the glass transition temperature Tg is more than 150 ℃, and the good form can be still kept when the film is baked after exposure; 5. has better chemical stability and anti-etching capability.
Alternatively, R 1 Selected from phenyl, pyrenyl, 1,2,3, 4-tetrahydro-1-naphthyl, 1,2,3, 4-tetrahydro-2-naphthyl, 1,2,3, 4-tetrahydro-1-methyl-2-naphthyl, 1,2,3, 4-tetrahydro-2-methyl-1-naphthyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-diisopropylphenyl, 2-chlorophenyl, 2-bromophenyl, cyclohexyl, methylcyclohexyl, adamantyl, methyladamantyl or quinuclidinyl.
R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from the group consisting of hydrogen, hydroxy, fluoro, chloro, bromo, iodo, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2-dimethyl-1-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-1-hexyl, 3-methyl-1-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, iodine, and mixtures thereof, 3-methyl-2-pentyl, 3-methyl-3-pentyl, 2-dimethyl-1-butyl, 3-dimethyl-2-butyl, 2, 3-dimethyl-1-butyl, 2, 3-dimethyl-2-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy or tert-butoxy.
R 7 、R 8 Each independently selected from methyl, ethyl, n-propyl, isopropyl,N-butyl, isobutyl, tert-butyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2-dimethyl-1-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-2-pentyl, 3-methyl-3-pentyl, 3-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-3-pentyl, 2-methyl-2-pentyl, and the like, 2, 2-dimethyl-1-butyl, 3-dimethyl-2-butyl, 2, 3-dimethyl-1-butyl or 2,3, -dimethyl-2-butyl.
Alternatively, R 1 Is cyclohexyl, R 2 、R 3 、R 5 And R 6 Are each hydrogen, R 4 Is hydroxy, R 7 And R 8 Are all methyl.
The content of the repeating unit formed by the first monomer in the copolymer is 20-60 wt%, the content of the repeating unit formed by the second monomer is 5-35 wt%, the content of the repeating unit formed by the third monomer is 10-45 wt%, and the content of the repeating unit formed by the fourth monomer is 10-40 wt%.
When the content of the first monomer and/or the third monomer is higher than the maximum value, the content of the corresponding fourth hydrophilic monomer is reduced, which leads to the dissolution of the copolymer in the conventional photoresist solvent propylene glycol methyl ether acetate, and does not meet the material requirements of the double-layer Lift-off stripping process. Similarly, when the fourth monomer content exceeds the upper limit, the hydrophilicity of the polymer is too high, resulting in a dissolution rate of the polymer in deionized water.
Optionally, the copolymer comprises 20 to 50 wt% of repeating units formed by the first monomer, 10 to 30 wt% of repeating units formed by the second monomer, 10 to 40 wt% of repeating units formed by the third monomer, and 10 to 35 wt% of repeating units formed by the fourth monomer.
Optionally, the copolymer has a content of repeating units derived from the first monomer of 30 to 50 wt%, a content of repeating units derived from the second monomer of 10 to 25 wt%, a content of repeating units derived from the third monomer of 15 to 35 wt%, and a content of repeating units derived from the fourth monomer of 10 to 30 wt%.
In one embodiment of the present application, the copolymer has a repeat unit content of 40 wt% for the first monomer, 15 wt% for the second monomer, 25 wt% for the third monomer, and 20 wt% for the fourth monomer. In some other embodiments herein, the copolymer can further include 20, 25, 30, 35, 45, 50, 55, or 60 weight percent of repeating units derived from the first monomer, 5, 10, 20, 25, 30, or 35 weight percent of repeating units derived from the second monomer, 10, 15, 20, 30, or 40 weight percent of repeating units derived from the third monomer, 10, 15, 25, 30, 35, or 40 weight percent of repeating units derived from the fourth monomer, and the sum of the first, second, third, and fourth monomers is 100 weight percent.
The weight average molecular weight of the copolymer is 5000-100000 g/mol.
Optionally, the weight average molecular weight of the copolymer is 10000-100000 g/mol.
Optionally, the weight average molecular weight of the copolymer is 10000-80000 g/mol.
Optionally, the weight average molecular weight of the copolymer is 10000-50000 g/mol.
In one embodiment of the present application, the weight average molecular weight of the copolymer is 20000 g/mol. In other embodiments of the present application, the weight average molecular weight of the copolymer can also be 5000g/mol, 10000g/mol, 15000g/mol, 25000g/mol, 30000g/mol, 35000g/mol, 40000g/mol, 45000g/mol, 50000g/mol, 55000g/mol, 60000g/mol, 65000g/mol, 70000g/mol, 75000g/mol, 80000g/mol, 85000g/mol, 90000g/mol, 95000g/mol, or 10000 g/mol.
The polydispersity of the copolymer is less than or equal to 3.5.
Alternatively, the copolymer has a polydispersity ≦ 3.
Alternatively, the copolymer has a polydispersity ≦ 2.5.
Alternatively, the copolymer has a polydispersity ≦ 2.
Optionally, the copolymer has a polydispersity of 1.5 to 2.
In one embodiment of the present application, the copolymer has a polydispersity of 2. In other embodiments of the present application, the polydispersity of the copolymer may also be 1.5, 1.6, 1.7, 1.8, 1.9, 2.1, 2.2, 2.5, 2.7, 3, 3.3, or 3.5.
The copolymers of the present application can be prepared by a free radical polymerization process comprising the steps of:
wherein, in the compound (1), R 2 ～R 6 At least one of them is a hydroxyl group; in the compound (2), R 2 ’ ～R 6 ’ At least one of which is an acetoxy group.
Wherein, in the polymer (1), R 2 ’ ～R 6 ’ At least one of them is an acetoxy group.
Wherein, in the polymer (2), R 2 ～R 6 At least one of which is a hydroxyl group.
The copolymer has the advantages of easily obtained polymerization monomers or raw materials, convenient production, simple and convenient free radical polymerization method and no need of special equipment and special synthesis environment.
The present application provides an underfill composition comprising an additive, a solvent, and the copolymer described above.
The primer composition of the present application can be applied to a substrate surface by methods including spin coating, spray coating, dip coating, and knife coating. The material of the substrate includes a semiconductor material.
The additives include surfactants and pigments.
Surfactants include fluorinated and/or non-fluorinated surfactants.
Optionally, the surfactant is a nonionic surfactant.
Optionally, the surfactant comprises a perfluoro C4 surfactant and/or a fluoro diol.
The pigment includes any one or more of an alkali-soluble pigment, a monoazo dye and a disazo dye containing one or more phenolic hydroxyl groups.
Alternatively, the alkali-soluble pigment comprises curcumin, the monoazo dye containing one or more phenolic hydroxyl groups comprises sudan orange G, and the disazo dye comprises 4, 4' -dihydroxyazobenzene.
The solvent includes any one or more of a polar amide solvent, a ketone solvent, a cyclic ether solvent, a cyclic ketone ether solvent and a polar hydroxy solvent.
Alternatively, the polar amide solvent comprises N, N-dimethylformamide and/or N-methylpyrrolidone, the ketone solvent comprises any one or more of cyclopentanone, 2-pentanone, and 2, 4-pentanedione, the cyclic ether solvent comprises 1, 3-dioxolane and/or tetrahydrofuran, the cyclic ketone ether solvent comprises gamma-butyrolactone, and the polar hydroxy solvent comprises tetrahydrofurfuryl alcohol.
The primer composition includes a solid component and a solvent, the solid component including a surfactant, a pigment, and the copolymer described above.
The solid component comprises 80-99 wt% of copolymer, 0.01-20 wt% of pigment and 0.01-20 wt% of surfactant.
Optionally, the solid component comprises 85 to 99 wt% of the copolymer, 0.05 to 15 wt% of the pigment and 0.05 to 15 wt% of the surfactant.
Optionally, the solid component comprises 90 to 99 wt% of the copolymer, 0.05 to 10 wt% of the pigment and 0.05 to 10 wt% of the surfactant.
The solid content of the primer composition is 5-15 wt%, and the solvent content is 85-95 wt%.
The application also provides a two-layer system, which comprises a top photoresist and a bottom photoresist formed by the bottom photoresist composition.
The bilayer system of the present application can be used in a bilayer lift-off process. Under the same exposure condition and the same developing condition, the dissolution rate of the bottom layer photoresist in the alkaline developing solution is faster than that of the top layer photoresist in the alkaline developing solution.
The top layer photoresist can be selected from photoresists such as C5315, C8325, C8315, C7510, C7500, C7310 of Beijing Corwa.
The dissolution rate of the primer in the alkaline developer can be adjusted by adjusting the baking temperature after exposure, the baking time after exposure and the concentration of the tetramethylammonium hydroxide developer.
Optionally, the dissolution rate of the bottom layer photoresist in the tetramethylammonium hydroxide developing solution is 20-50 nm/s, and the dissolution rate of the top layer photoresist in the tetramethylammonium hydroxide developing solution is less than or equal to 48 nm/s.
Optionally, the dissolution rate of the bottom layer photoresist in the tetramethylammonium hydroxide developing solution is 20-50 nm/s, and the dissolution rate of the top layer photoresist in the tetramethylammonium hydroxide developing solution is less than or equal to 45 nm/s.
The application also provides an application of the double-layer system in a double-layer stripping process, and the double-layer system is exposed and developed.
Optionally, the exposure is a single exposure.
Alternatively, the development is a single development.
The double-layer system can obtain the target photoetching pattern only by single development and single development, and the photoetching efficiency is greatly improved.
Optionally, the post-exposure baking temperature is 150-200 ℃;
optionally, the baking time after exposure is 2-5 min;
optionally, the developing solution used for developing comprises tetramethylammonium hydroxide developing solution;
optionally, the concentration of the tetramethylammonium hydroxide developer is 1.19 wt% to 2.38 wt%.
A copolymer, primer composition, two-layer system and its application in a two-layer lift-off process of the present application are described in further detail below with reference to the examples.
Example 1
The embodiment of the application provides a copolymer and a preparation method thereof.
1. The structural formula of copolymer A1 is as follows:
2. process for producing copolymer
(1) Synthesis of N- (4-acetoxyphenyl) maleimide
9.8g (0.10mol) of maleic anhydride and 50mL of acetone are respectively added into a three-neck flask provided with a stirring rod and a reflux condenser tube, stirred until the maleic anhydride and the acetone are completely dissolved, and a mixed solution of 10.9g (0.10mol) of p-aminophenol and 20mL of acetone is slowly dripped into the three-neck flask by a dropping funnel under ice water bath, so that a large amount of yellow precipitate appears. Removing the cooling device, heating to 50 ℃, refluxing for 1h, cooling to room temperature after 1h, supplementing 15mL triethylamine, 20mL acetic anhydride and 3.0g nickel acetate, enabling the system to be blue-green, continuously refluxing for 5h to obtain a dark green system, cooling, pouring into a large amount of cold water under vigorous stirring, generating yellow precipitate, performing suction filtration, washing to be neutral, performing vacuum drying to obtain yellow powder solid, and recrystallizing by using methylbenzene, wherein the reaction formula is as follows:
(2) synthesis of Poly (N-cyclohexylmaleimide-co-N- (4-acetoxyphenyl) maleimide-co-methyl methacrylate-co-hydroxyethyl methacrylate)
40g (0.22mol) of N-cyclohexylmaleimide, 25g (0.11mol) of N- (4-acetoxyphenyl) maleimide, 15g (0.15mol) of methyl methacrylate and 20g (0.15mol) of hydroxyethyl methacrylate were placed in a three-necked flask, 500g of DMF solvent was added, nitrogen gas was introduced to remove air, and dissolution was carried out with stirring. 1g of initiator Azobisisobutyronitrile (AIBN) after recrystallization is added into the mixed solution, the temperature is raised to 70 ℃ by a constant temperature oil bath, and the polymerization is carried out for 24 hours under the protection of nitrogen. Taking out and cooling to room temperature, slowly adding the reaction solution into 1500mL of ether, separating out white precipitate, carrying out suction filtration, dissolving again, and repeatedly washing for three times. The white precipitate from the final treatment was dried in a vacuum oven to give 86g of product, of the formula:
(3) synthesis of Poly (N-cyclohexylmaleimide-co-N- (4-hydroxyphenyl) maleimide-co-methyl methacrylate-co-hydroxyethyl methacrylate
Dissolving 5.0g of poly (N-cyclohexylmaleimide) co-N- (4-acetoxyphenyl) maleimide-co-methyl methacrylate-co-hydroxyethyl methacrylate) synthesized in the step (2) in 30mL of DMF, adding 15mL of ammonia water into the DMF solution, heating to be completely dissolved, boiling for 5min, cooling to room temperature, adding diluted hydrochloric acid under stirring until the pH value is 2-3, allowing precipitation to occur again, performing suction filtration, washing with deionized water to be neutral, and performing vacuum drying to obtain a final product, wherein the weight average molecular weight of the obtained polymer is 25690g/mol, the molecular weight distribution coefficient D is 2.05, and the reaction formula is as follows:
example 2
The embodiment of the application provides a copolymer and a preparation method thereof.
1. The structural formula of copolymer A2 is as follows:
2. process for producing copolymer
(1) Synthesis of N- (3-acetoxyphenyl) maleimide
In a three-necked flask equipped with a stirring rod and a reflux condenser, 3.92g (0.04mol) of maleic anhydride, 4.7g (0.43mol) of 3-aminophenol and 250ml of glacial acetic acid were added, respectively, and the mixture was heated in an oil bath and reacted at 120 ℃ for 5 hours. After the reaction, the reaction mixture was cooled to room temperature, 50ml of distilled water and 1000ml of ethyl acetate were added to the reaction mixture, the layers were separated, the organic phase was washed with a saturated sodium bicarbonate solution (300ml) 3 times, dried over magnesium sulfate, filtered under suction, and the organic solvent was removed by rotary evaporation to give N- (3-hydroxyphenyl) maleimide.
Placing 18.92g (0.1mol) of N- (3-hydroxyphenyl) maleimide and 40ml of acetone into a three-neck flask, stirring for dissolving, heating for refluxing, supplementing 15ml of triethylamine, 20ml of acetic anhydride and 3.0g of nickel acetate after 1h, continuously refluxing for 4h, cooling after the reaction is finished, pouring into a large amount of cold water under vigorous stirring, generating brown precipitate, performing suction filtration, washing to be neutral, drying in vacuum, recrystallizing by using toluene, and obtaining the yield of 65 percent, wherein the reaction formula is as follows:
(2) synthesis of Poly (N-cyclohexylmaleimide-co-N- (3-acetoxyphenyl) maleimide-co-methyl methacrylate-co-hydroxyethyl methacrylate)
N-cyclohexylmaleimide (40g, 0.22mol), N- (3-acetoxyphenyl) maleimide (25g, 0.11mol), methyl methacrylate (15g, 0.15mol) and hydroxyethyl methacrylate (20g, 0.15mol) were placed in a three-necked flask, 500g of DMF solvent was added, nitrogen gas was introduced to exclude air, and dissolved with stirring. And weighing 1g of initiator AIBN after recrystallization treatment, adding the initiator AIBN into the mixed solution, raising the temperature to 70 ℃ in a constant-temperature oil bath, and polymerizing for 24 hours under the protection of nitrogen. Taking out and cooling to room temperature, slowly adding the reaction solution into 1500mL of ether, separating out white precipitate, carrying out suction filtration, dissolving again, and repeatedly washing for three times. The white precipitate from the final treatment was dried in a vacuum oven and weighed to give 90g of product, the reaction formula is as follows:
(3) synthesis of Poly (N-cyclohexylmaleimide-co-N- (3-hydroxyphenyl) maleimide-co-methyl methacrylate-co-hydroxyethyl methacrylate)
Taking 5.0g of poly N-cyclohexylmaleimide-co-N- (3-acetoxyphenyl) maleimide-co-methyl methacrylate-co-hydroxyethyl methacrylate synthesized in the previous step, dissolving in 30mL of mixed solution of tetrahydrofuran, dropwise adding 15mL of ammonia water into the mixed solution to cause precipitation, heating the mixed solution to be completely dissolved, boiling the mixed solution for 5min, cooling the mixed solution to room temperature, adding dilute hydrochloric acid into the mixed solution under stirring until the pH value is 2-3, causing precipitation to occur again, performing suction filtration, washing the mixed solution to be neutral by deionized water, and performing vacuum drying to obtain a final product with the yield of 60%. The weight average molecular weight of the obtained polymer was 20196g/mol, the molecular weight distribution coefficient D was 1.69, and the reaction formula was as follows:
example 3
The embodiment of the application provides a copolymer and a preparation method thereof.
1. The structural formula of copolymer A3 is as follows:
2. process for producing copolymer
(1) Synthesis of N- (2-acetoxyphenyl) maleimide
In a three-necked flask equipped with a stirring rod and a reflux condenser, 15.0g (0.15mol) of maleic anhydride, 16.7g (0.15mol) of 2-aminophenol and 50ml of Dimethylformamide (DMF) were charged, respectively, and ice-cooled, after which 7.5g of phosphorus pentoxide and 4g of concentrated sulfuric acid were slowly added thereto, and after 30 minutes of reaction, the reaction apparatus was moved to an oil bath and heated at 70 ℃ for 6 hours. After the reaction is finished, pouring the reaction solution into 150ml of deionized water to obtain a large amount of precipitate, washing the precipitate with water, filtering and drying to obtain the N- (2-hydroxyphenyl) maleimide with the yield of 80%.
Placing 18.92g (0.1mol) of N- (3-hydroxyphenyl) maleimide and 40ml of acetone in a three-neck flask, stirring for dissolving, heating for refluxing, supplementing 15ml of triethylamine, 20ml of acetic anhydride and 3.0g of nickel acetate after 1h, continuously refluxing for 4h, cooling after the reaction is finished, pouring into a large amount of cold water under vigorous stirring, generating brown precipitate, performing suction filtration, washing to be neutral, drying in vacuum, recrystallizing by using toluene, and obtaining the yield of 55 percent, wherein the reaction formula is as follows:
(2) synthesis of Poly (N-cyclohexylmaleimide-co-N- (2-acetoxyphenyl) maleimide-co-methyl methacrylate-co-hydroxyethyl methacrylate)
The reaction scheme was as follows, except that N- (4-acetoxyphenyl) maleimide in the step (2) in example 1 was replaced with N- (2-acetoxyphenyl) maleimide and the other steps were the same as in the step (2) in example 1:
(3) synthesis of Poly (N-cyclohexylmaleimide-co-N- (2-hydroxyphenyl) maleimide-co-methyl methacrylate-co-hydroxyethyl methacrylate)
The procedure of (3) in example 1 was otherwise the same as that of (3) in example 1 except that poly (N-cyclohexylmaleimide-co-N- (4-acetoxyphenyl) maleimide-co-methyl methacrylate-co-hydroxyethyl methacrylate) was replaced with poly (N-cyclohexylmaleimide-co-N- (2-acetoxyphenyl) maleimide-co-methyl methacrylate-co-hydroxyethyl methacrylate. The weight average molecular weight of the obtained polymer was 17121g/mol, the molecular weight distribution coefficient D was 1.82, and the reaction formula was as follows:
comparative example 1
The comparative example of the present application provides a copolymer and a method for preparing the same.
1. The structural formula of copolymer B1 is as follows:
2. process for producing copolymer
Maleic anhydride (34.21g, 0.35mol), methyl methacrylate (60.07g, 0.6mol) and methacrylic acid (5g, 0.05mol) were placed in a three-necked flask, 500g of 1, 4-dioxane solvent was added, nitrogen gas was introduced to remove air, and the mixture was dissolved with stirring. And weighing 2.96g of initiator AIBN after recrystallization treatment, adding the initiator AIBN into the mixed solution, raising the temperature to 70 ℃ in a constant-temperature oil bath, and polymerizing for 24 hours under the protection of nitrogen. Taking out and cooling to room temperature, slowly adding the reaction solution into 1000mL of ether, separating out white precipitate, carrying out suction filtration, dissolving again, and repeatedly washing for three times. The white precipitate from the final treatment was dried in a vacuum oven and weighed to yield 84g of product according to the following reaction scheme:
comparative example 2
The comparative example of the present application provides a copolymer and a method for preparing the same.
1. The structural formula of copolymer B2 is as follows:
2. preparation method of copolymer B2
N-vinylpyrrolidone (14.71g,0.15mol), maleic anhydride (44.46g, 0.40mol), methyl methacrylate (40.04g, 0.40mol) and methacrylic acid (4.30g, 0.05mol) were placed in a three-necked flask, 500g of an ethyl lactate solvent was added, nitrogen gas was introduced to remove air, and dissolved with stirring. 3.08g of initiator AIBN after recrystallization treatment is weighed and added into the mixed solution, the temperature is raised to 70 ℃ by a constant temperature oil bath, and polymerization is carried out for 24 hours under the protection of nitrogen. Taking out and cooling to room temperature, slowly adding the reaction solution into 1500mL of ether, separating out white precipitate, carrying out suction filtration, dissolving again, and repeatedly washing for three times. The white precipitate from the final treatment was dried in a vacuum oven and weighed to give 87g of product, according to the following reaction scheme:
comparative example 3
The comparative example of the present application provides a copolymer and a method for preparing the same.
1. The structural formula of copolymer B3 is as follows:
2. preparation method of copolymer B3
N-vinylpyrrolidone (14.71g,0.15mol), maleic anhydride (50.01g, 0.45mol) and methyl methacrylate (40.04g, 0.40mol) were placed in a three-necked flask, 500g of an ethyl lactate solvent was added, nitrogen gas was introduced to remove air, and dissolution was carried out with stirring. 3.08g of initiator AIBN after recrystallization treatment is weighed and added into the mixed solution, the temperature is raised to 70 ℃ by a constant temperature oil bath, and polymerization is carried out for 24 hours under the protection of nitrogen. Taking out and cooling to room temperature, slowly adding the reaction solution into 1500mL of ether, separating out white precipitate, carrying out suction filtration, dissolving again, and repeatedly washing for three times. The white precipitate obtained in the final treatment was dried in a vacuum oven and weighed to give a polymerization yield of 80%, according to the following reaction scheme:
test example 1
The copolymers prepared in examples 1 to 3 and comparative examples 1 to 3 were mixed with cyclopentanone to prepare solutions having a solid content of 20 wt%, the solutions were coated on blank silicon wafers respectively by a spin coater, the silicon wafers were baked on a hot plate at 180 ℃ for 300s, developed with 2.38 wt% (0.26N) alkaline developer for 10s, the film thickness of the polymer on the surface of the silicon wafers before and after development was measured by a film thickness measuring instrument, and the polymer film remaining rate was calculated as shown in Table 1.
TABLE 1 film remaining Rate on silicon wafer for examples 1 to 3 and comparative examples 1 to 3
| Sample (I) | Film retention rate |
| Example 1(A1) | 88％ |
| Example 2(A2) | 90％ |
| Example 3(A3) | 94％ |
| COMPARATIVE EXAMPLE 1(B1) | 0 |
| COMPARATIVE EXAMPLE 2(B2) | 0 |
| COMPARATIVE EXAMPLE 3(B3) | 0 |
As can be seen from Table 1, the film retention rate of the copolymer obtained in examples 1 to 3 of the present application is high, i.e., the dissolution rate of the copolymer in the developer is moderate, while the film retention rate of the copolymer obtained in comparative examples 1 to 3 is 0, i.e., the dissolution rate of the copolymer in the developer is too fast to control.
Test example 2
Starting from the copolymers of examples 1 and 1, an underlayer gum was prepared comprising 9% by weight of copolymer A1, 0.5% by weight of surfactant, 0.5% by weight of pigment and 90% by weight of cyclopentanone, and a PMGI gum solution commercially available from MicroChem. A layer of uniform bottom layer adhesive is coated on a clean silicon wafer firstly, the film thickness is 0.5 mu m, and the pre-baking is carried out at 180 ℃/300 s. After baking, the product KMP C5315 ultraviolet positive photoresist is coated, the photoresist is I-line photoresist, the resolution of 0.5 mu m can be realized, the coating film thickness is 1.15 mu m, and the pre-baking is carried out at 90 ℃/60 s. The developing solution is 2.38 wt% TMAH developing solution, and the developing time is 60 s.
Using an automatic spin coater MarkV to perform the processes of gluing, baking, developing and the like;
exposure was carried out using a Nikon i9 stepper exposure machine;
the line cross-sectional morphology was observed using SEM4800 from HITACHI.
FIG. 2 is a graph of the topography of an underlayer adhesive formed of the A1 copolymer of the present application and a KMP C5315 UV positive photoresist, and FIG. 3 is a graph of the topography of PMGI and KMP C5315 UV positive photoresists commercially available from MicroChem corporation. It is evident that the copolymer a1 of example 1 of the present application can achieve a similar lithographic cross-sectional profile to PMGI commercially available from MicroChem corporation. That is, the cross-sectional profile formed by the bottom layer photoresist formed by the a1 copolymer in example 1 of the present application and the top layer photoresist can meet the requirement of the double layer stripping process.
The foregoing is illustrative of the present application and is not to be construed as limiting thereof, as numerous modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (22)
1. A copolymer is characterized in that the copolymer is obtained by free radical polymerization of a first monomer, a second monomer, a third monomer and a fourth monomer;
the chemical formulas of the first monomer, the second monomer, the third monomer and the fourth monomer are sequentially as follows:
wherein R is 1 Selected from unsubstituted or substituted C 6-18 Aryl, unsubstituted or substituted C 6-18 A cycloalkyl group;
R 2 、R 3 、R 4 、R 5 、R 6 each independently selected from hydrogen, hydroxy, halogen, C 1-6 Alkyl or C 1-6 Alkoxy, and R 2 、R 3 、R 4 、R 5 、R 6 At least one of which is a hydroxyl group;
R 7 、R 8 each independently selected from unsubstituted or substituted C 1-6 An alkyl group;
substituted C 6-18 Aryl, substituted C 1-6 Alkyl and substituted C 1-6 The substituents of the alkyl are respectively and independently selected from halogen and C 1-4 Alkyl or C 1-4 An alkoxy group;
the weight average molecular weight of the copolymer is 5000-100000 g/mol, the polydispersity is less than or equal to 3.5, the content of a repeating unit formed by the first monomer in the copolymer is 20-60 wt%, the content of a repeating unit formed by the second monomer is 5-35 wt%, the content of a repeating unit formed by the third monomer is 10-45 wt%, and the content of a repeating unit formed by the fourth monomer is 10-40 wt%.
2. The copolymer of claim 1, wherein R is 1 Selected from phenyl, pyrenyl, 1,2,3, 4-tetrahydro-1-naphthyl, 1,2,3, 4-tetrahydro-2-naphthyl, 1,2,3, 4-tetrahydro-1-methyl-2-naphthyl, 1,2,3, 4-tetrahydro-2-methyl-1-naphthyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-diisopropylphenyl, 2-chlorophenyl, 2-bromophenyl, cyclohexyl, methylcyclohexyl, adamantyl, methyladamantyl or quinuclidinyl;
R 2 、R 3 、R 4 、R 5 、R 6 each independently selected from the group consisting of hydrogen, hydroxy, fluoro, chloro, bromo, iodo, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2-dimethyl-1-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-1-hexyl, 3-methyl-1-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, iodine, and mixtures thereof, 3-methyl-2-pentyl, 3-methyl-3-pentyl, 2-dimethyl-1-butyl, 3-dimethyl-2-butyl, 2, 3-dimethyl-1-butyl, 2, 3-dimethyl-2-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy or tert-butoxy;
R 7 、R 8 each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2-dimethyl-1-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-2-pentyl, n-butyl, isobutyl, tert-butyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-pentyl, 2-hexyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-pentyl, and mixtures thereof, 3-methyl-3-pentyl, 2-dimethyl-1-butyl, 3-dimethyl-2-butyl, 2, 3-dimethyl-1-butyl or 2,3, -dimethyl-2-butyl.
3. The copolymer of claim 1, wherein R is 1 Is cyclohexyl, said R 2 The R is 3 The R is 5 And said R 6 Are all hydrogen, said R 4 Is hydroxy, said R 7 And said R 8 Are all methyl.
4. The copolymer of any one of claims 1 to 3, wherein the copolymer comprises 20 to 50 wt% of the repeating units derived from the first monomer, 10 to 30 wt% of the repeating units derived from the second monomer, 10 to 40 wt% of the repeating units derived from the third monomer, and 10 to 35 wt% of the repeating units derived from the fourth monomer.
5. The copolymer of claim 4, wherein the copolymer comprises 30 to 50 wt% of the repeating units derived from the first monomer, 10 to 25 wt% of the repeating units derived from the second monomer, 15 to 35 wt% of the repeating units derived from the third monomer, and 10 to 30 wt% of the repeating units derived from the fourth monomer.
6. The copolymer according to any one of claims 1 to 3, wherein the copolymer has a weight average molecular weight of 10000 to 100000 g/mol.
7. The copolymer of claim 6, wherein the copolymer has a weight average molecular weight of 10000 to 80000 g/mol.
8. The copolymer of claim 6, wherein the copolymer has a weight average molecular weight of 10000 to 50000 g/mol.
9. A copolymer according to any of claims 1 to 3, wherein the copolymer has a polydispersity index of 3 or less.
10. The copolymer of claim 9, wherein the copolymer has a polydispersity of 2.5 or less.
11. The copolymer of claim 9, wherein the copolymer has a polydispersity index of 2 or less.
12. An underfill composition comprising an additive, a solvent and the copolymer of any one of claims 1 to 11.
13. The underfill composition of claim 12, wherein the additive comprises a surfactant and a pigment.
14. A bilayer system comprising a top photoresist and a primer formed from the primer composition of claim 12 or 13.
15. The bilayer system of claim 14, wherein the bottom layer photoresist dissolves at a faster rate in an alkaline developer than the top layer photoresist dissolves at the same exposure conditions and the same development conditions in an alkaline developer.
16. Use of a bilayer system according to claim 14 or 15 in a bilayer lift-off process wherein the bilayer system is exposed and developed.
17. Use of a bilayer system according to claim 16 in a bilayer lift-off process wherein the exposure is a single exposure.
18. Use of a bilayer system according to claim 16 in a bilayer lift-off process wherein the development is a single development.
19. The use of a bilayer system according to claim 16 in a bilayer lift-off process wherein the post exposure bake temperature is 150 to 200 ℃.
20. The use of a bilayer system according to claim 19 wherein the post exposure bake time is 2-5 min.
21. Use of a bilayer system according to claim 16 in a bilayer lift-off process wherein the developing solution comprises a tetramethylammonium hydroxide developing solution.
22. Use of a bilayer system according to claim 16 in a bilayer lift-off process wherein the concentration of tetramethylammonium hydroxide developer is from 1.19 wt% to 2.38 wt%.
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