Ester-type photosensitive polyimide composite material, preparation method and semiconductor device

Abstract

The ester-type photosensitive polyimide material and its preparation method provided by this application reduce the dielectric constant by introducing fluorinated graphene quantum dots containing low-polarity fluorine atoms. Because fluorine atoms have strong electronegativity, they can firmly fix electrons, thereby reducing the polarizability; the small-sized, large-specific-surface-area fluorinated graphene quantum dots are easier to evenly disperse in the photosensitive polyimide matrix, thereby improving its overall performance and reducing the dielectric constant; and the fluorinated groups are hydrophobic, which can also prevent the material from degrading due to water absorption. In addition, by adjusting the proportion of methacrylate groups, reaction temperature, and time, the molecular weight and grafting rate are controlled to achieve its high sensitivity. In addition, this application also provides a semiconductor device including the ester-type photosensitive polyimide material.

Description

Technical Field

[0001] The present application relates to the field of photosensitive polyimide materials, and in particular to an ester-type photosensitive polyimide composite material, a preparation method, and a semiconductor device. Background Art

[0002] Due to its excellent overall performance, polyimide is widely used as a surface protective layer and interlayer dielectric in semiconductor devices. However, traditional polyimide lacks photosensitivity, requiring these applications to be coated with a photoresist, patterned, and then etched to transfer the pattern to the polyimide. Therefore, photosensitive polyimides with direct patterning capabilities have attracted widespread attention due to their potential to simplify the integrated circuit manufacturing process and reduce processing costs. The rapid decrease in high-frequency communications and integrated circuit package size and device pin pitch has increased the demand for dielectric materials, including a low dielectric constant (<3.5). This is because the development of high-frequency communications and the trend towards device miniaturization can lead to signal transmission delays, loss, and crosstalk. In addition to a low dielectric constant, good thermal and mechanical properties, hydrophobicity, and chemical inertness are also required to ensure device reliability. Therefore, photosensitive polyimides with a low dielectric constant and excellent overall performance are urgently needed to meet these technological developments.

[0003] Currently, most photosensitive polyimides focus on chemical amplification systems and doped photoinitiators. While these technologies offer high photosensitivity and resolution, the small molecules doped with them significantly impact the mechanical strength and heat resistance of the photosensitive polyimide itself. Furthermore, while the dielectric constant of photosensitive polyimides can be reduced by adding fillers (such as fluorinated graphene and polyethylene propylene), large fillers tend to aggregate within the photosensitive polyimide matrix, compromising both the mechanical and photosensitivity properties of the photosensitive polyimide. Summary of the Invention

[0004] In view of this, it is necessary to provide an ester-type photosensitive polyimide composite material with a low dielectric constant, excellent photosensitivity, mechanical properties, good hydrophobicity and heat resistance, and a preparation method thereof to address the defects in the prior art.

[0005] To solve the above problems, this application adopts the following technical solutions:

[0006] One of the purposes of this application is to provide an ester-type photosensitive polyimide composite material, comprising the following components:

[0007] (A) component: polyamic acid ester;

[0008] (B) ingredient: photoinitiator;

[0009] (C) component: a cross-linking agent;

[0010] (D) ingredient: fluorinated graphene quantum dots; and

[0011] (E) Component: solvent.

[0012] In some embodiments, the content of the component (B) is 0.5 to 5 parts by mass relative to 100 parts by mass of the component (A).

[0013] In some embodiments, the content of the component (C) is 5 to 25 parts by mass relative to 100 parts by mass of the component (A).

[0014] In some embodiments, the content of the component (D) is 0.1 to 1 part by mass relative to 100 parts by mass of the component (A).

[0015] In some embodiments, the (B) includes: GC-410, OXE01, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone and other acetophenone derivatives, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone and other thioxanthone derivatives, benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl ketal and other benzyl derivatives, benzoin, benzoin methyl ether and other benzyl derivatives. At least one of oximes such as an indium derivative, 1-phenyl-1,2-butanedione-2-(0-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(0-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(0-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(0-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(0-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(0-benzoyl)oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl peroxide, and aromatic biimidazoles.

[0016] In some embodiments, the (C) comprises: tetraethylene glycol dimethacrylate, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-isopropylimidazole, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, triethylenetetramine, dimethylaminopropylamine, diethylaminopropylamine, ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC, isopropylimidazole, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, triethylenetetramine, dimethylaminopropylamine, diethylaminopropylamine, ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC, DM-BI25X-F, 46DM℃, 46DMOIPP, 46DMOEP, DML-MBPC, DML-MB℃, DML-℃HP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-℃, dimethylol-Bis-C, dimethylol-Bis℃-P, DML-Bis℃-Z, At least one of DML-Bis HP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, and DML-Bis25X-PCHP.

[0017] In some embodiments, the (E) includes: one or a combination of at least two of N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP) or N,N-dimethylformamide (DMF), tetrahydrofuran, m-cresol, γ-butyrolactone, tetramethylurea, dimethyl sulfoxide, hexamethylphosphoric acid triamide, and chloroform.

[0018] The second object of this application is to provide a method for preparing the ester-type photosensitive polyimide composite material, comprising the following steps:

[0019] dissolving fluorinated graphene quantum dots in the solvent, performing ultrasonic treatment for 30-90 minutes, and then adding the photoinitiator, the crosslinking agent, and polyamic acid ester to obtain a fluorinated graphene quantum dot / polyamic acid ester composite solution;

[0020] Applying the fluorinated graphene quantum dots / polyamic acid ester composite solution on the surface of a substrate, and then exposing and developing the solution to form a pattern;

[0021] The pattern is subjected to thermal imidization treatment to obtain the ester-type photosensitive polyimide composite material.

[0022] In some embodiments, in the step of dissolving the fluorinated graphene quantum dots in the solvent, ultrasonically treating for 30-90 minutes, and then adding the photoinitiator, the crosslinker, and the polyamic acid ester to obtain the fluorinated graphene quantum dots / polyamic acid ester composite solution, the fluorinated graphene quantum dots are prepared by the following method:

[0023] The fluorinated carbon source is placed in an organic solvent, and then ultrasonic treatment is performed. After standing, the supernatant is taken out and centrifuged. After centrifugation, the supernatant is taken out to remove the organic solvent, and finally dried to obtain fluorinated graphene quantum dots.

[0024] In some embodiments, the carbon source includes at least one of fluorinated carbon fibers, fluorinated graphene, fluorinated carbon, and fluorinated carbon nanotubes.

[0025] In some embodiments, in the step of dissolving the fluorinated graphene quantum dots in the solvent, ultrasonically treating for 30-90 minutes, and then adding the photoinitiator, the crosslinking agent, and the polyamic acid ester to obtain the fluorinated graphene quantum dots / polyamic acid ester composite solution, the polyamic acid ester is prepared by the following method:

[0026] Under a nitrogen atmosphere, at a temperature of 40-45° C., mixing dianhydride, hydroxyethyl methacrylate, pyridine and an organic solvent for reaction for 2-10 hours to obtain a mixed solution;

[0027] In a nitrogen atmosphere at 0° C., adding diamine to the mixed solution and stirring for 5-10 hours to perform a polycondensation reaction to form a hydroxyethyl methacrylate-terminated polyamic acid solution;

[0028] While maintaining the temperature and atmosphere, trifluoroacetic anhydride is added to the polyamic acid solution and stirred for 0.5-3 hours to effect isoimidization;

[0029] Maintaining the mixture under a nitrogen atmosphere, at a temperature of 50-55° C., adding hydroxyethyl methacrylate to the isoimidized polyamic acid solution and stirring for 8-12 hours to form a photosensitive polyimide precursor solution;

[0030] The photosensitive polyimide precursor solution is dropped into deionized water to remove unreacted substances, and then filtered and dried to obtain the polyamic acid ester.

[0031] In some embodiments, the dianhydride includes pyromellitic dianhydride, maleic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3,4,4-diphenylsulfone tetracarboxylic dianhydride, 4,4'-terephthalic anhydride, hexafluorodianhydride, 1,2-ethylenebis[1,3-dihydro-1,3- At least one of dioxoisobenzofuran-5-carboxylate, bisphenol A dianhydride, glycerol bis(anhydrotrimellitate) acetate, 2,3,3',4'-biphenyltetracarboxylic dianhydride, p-phenylene-bis(trimellitate) dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 4,4'-(ethynyl-1,2-diyl)diphthalic anhydride, and 4,4'-thiodiphthalic anhydride.

[0032] In some embodiments, the diamine includes 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, aminopropyl di-terminated polydimethylsiloxane, 3,5-diamino-1,2,4-triazole, diaminopyridine, 2-(4-aminophenyl)-5-aminobenzimidazole, 2,2'-bis[4-(4-aminophenoxyphenyl)]propane, 2-amino-4-[(3,4-diaminophenyl)sulfonyl]aniline, 6,6'-bisamino-3,3'-methylenedibenzoic acid, 1-hydrogen-indazole-4,7-diamine, 7-nitro-1H-indazole-4-amine, 2,2'-diamino-4,4'-bithiazole, 3,6-Diaminocarbazole, methyl 2-(3,6-diamino-9H-carbazole-9-yl)acetate, 2,5-diaminobenzothiazole, 2,6-benzothiazole diamine, tert-butyl (6-amino-4-methylbenzo[D]thiazol-2-yl)carbamate, 4-methoxy-1,3-benzothiazole-2,6-diamine, benzoguanamine, 2,4-diamino-6-(2-fluorophenyl)-1,3,5-triazine, 2,4-diamino-6-(4-chlorophenyl)-1,3,5-triazine, 2,4-diamino-6-[4-(trifluoromethyl)phenyl]-1,3,5-triazine, 2,4-diamino-6-(3-fluorophenyl)-1,3,5-triazine, 2,4-diamino-6-[3-(trifluoromethyl)phenyl]-1,3,5-triazine At least one of triazine, 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine, 2,4-diamino-6-(3,5-difluorophenyl)-1,3,5-triazine, 2,4-diamino-6-(4-bromophenyl)-1,3,5-triazine, 2,4-diamino-6-(4-methoxyphenyl)-1,3,5-triazine, 2,3-diaminophenolazine, methylguanamine, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-thiazine, 4,6-diaminopyrimidine, or various nitrogen-containing heterocyclic rings, siloxanes, thioethers and other diamines.

[0033] In some embodiments, the organic solvent includes one or a combination of at least two of N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP) or N,N-dimethylformamide (DMF), tetrahydrofuran, m-cresol, γ-butyrolactone, tetramethylurea, dimethyl sulfoxide, hexamethylphosphoric acid triamide, and chloroform.

[0034] In some embodiments, the step of applying the fluorinated graphene quantum dot / polyamic acid ester composite solution on the surface of the substrate and then exposing and developing the composite solution to form a pattern specifically includes the following steps:

[0035] Spin coating the fluorinated graphene quantum dots / polyamic acid ester composite solution on the surface of the substrate;

[0036] The spin-coated substrate was soft-baked at 100°C for 3-10 minutes to remove part of the organic solvent to obtain a spin-coated film with a thickness of 2-5 μm;

[0037] performing an exposure process on the substrate based on the spin-coated film;

[0038] The exposed substrate is developed to form a line pattern.

[0039] In some embodiments, the step of performing thermal imidization treatment on the pattern to obtain the ester-type photosensitive polyimide composite material specifically includes:

[0040] Under a nitrogen atmosphere, the pattern was thermally imidized by a step-by-step heating method, wherein the step-by-step heating method was 100°C for 1 hour, 200°C for 1 hour, 300°C for 1 hour, and 350°C for 1 hour, with a heating rate of 2-10°C / minute. The pattern was then cooled to room temperature, and the pattern was peeled off from the substrate to obtain an ester-type photosensitive polyimide composite material with a low dielectric constant.

[0041] A third object of the present application is to provide a semiconductor device comprising a copper wiring and an insulating layer disposed on the copper wiring, wherein the insulating layer comprises the ester-type photosensitive polyimide composite material.

[0042] This application adopts the above technical solution, and its beneficial effects are as follows:

[0043] The ester-type photosensitive polyimide and its preparation method provided herein reduce the dielectric constant by introducing fluorinated graphene quantum dots containing low-polarity fluorine atoms. Fluorine atoms have strong electronegativity and can firmly fix electrons, thereby reducing polarizability. The small size and large specific surface area of ​​fluorinated graphene quantum dots make them easier to disperse evenly in the photosensitive polyimide matrix, thereby improving its overall performance and reducing the dielectric constant. Furthermore, the hydrophobicity of the fluorinated groups can also prevent the material from degrading due to water absorption. Furthermore, the molecular weight and grafting rate are controlled by adjusting the ratio of methacrylate groups, reaction temperature, and time, thereby achieving high sensitivity.

[0044] The ester-type photosensitive polyimide provided in this application has excellent comprehensive properties and has good application prospects in advanced packaging technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following briefly introduces the drawings required for use in the embodiments of the present application or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0046] Figure 1 This is a flow chart of the steps of the method for preparing the ester-type photosensitive polyimide composite material provided in this application.

[0047] Figure 2 This is a flow chart of the steps of the polyamic acid ester preparation method provided in this application.

[0048] Figure 3 A flow chart of the steps for forming a pattern provided in this application.

[0049] Figure 4 This is the XPS graph of the fluorinated graphene quantum dots provided in Example 1 of the present application.

[0050] Figure 5 This is a TEM image of the fluorinated graphene quantum dots provided in Example 1 of the present application.

[0051] Figure 6 The dielectric constants of the Pure PSPI film and the FCQD-PSPI composite film provided in Example 1 of the present application.

[0052] Figure 7 These are the stress-strain curves of the Pure-PSPI film and the FCQD-PSPI composite film provided in Example 1 of the present application.

[0053] Figure 8 100mJ / cm provided in Example 1 of this application 2 PSPI 3D confocal image after exposure. DETAILED DESCRIPTION

[0054] The following describes in detail embodiments of the present application, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present application, and should not be construed as limiting the present application.

[0055] In the description of this application, it should be understood that the terms "upper", "lower", "horizontal", "inside", "outside", etc., indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing this application and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on this application.

[0056] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of the technical features being referred to. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features. Throughout the description of this application, "plurality" means two or more, unless otherwise specifically defined.

[0057] In order to make the purpose, technical solutions and advantages of this application more clear, this application is further described in detail below with reference to the accompanying drawings and embodiments.

[0058] An ester-type photosensitive polyimide composite material provided in one embodiment of the present application includes the following components:

[0059] (A) component: polyamic acid ester;

[0060] (B) ingredient: photoinitiator;

[0061] (C) component: a cross-linking agent;

[0062] (D) ingredient: fluorinated graphene quantum dots; and

[0063] (E) Component: solvent.

[0064] In some embodiments, the content of the component (B) is 0.5 to 5 parts by mass relative to 100 parts by mass of the component (A).

[0065] Further, the (B) includes at least one of benzophenone derivatives, acetophenone derivatives, thioxanthone derivatives, benzyl derivatives, benzyl derivatives, benzoin derivatives, oximes, N-arylglycines, peroxides, and aromatic biimidazoles, and the benzophenone derivatives include GC-410, OXE01, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone; the thioxanthone derivatives include thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone; the benzil derivatives include benzil, benzil dimethyl ketal, benzil-β-methoxyethyl ketal; the benzoin derivatives include benzoin, benzoin methyl ether; the oximes include 1-phenyl-1,2-butanedione-2-(0-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(0-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(0-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(0-benzoyl) oxime, 1,3-diphenylpropanetrione-2-(0-ethoxycarbonyl) oxime, 1-phenyl-3- Ethoxypropanetrione-2-(O-benzoyl)oxime; the N-arylglycines include N-phenylglycine; the peroxides include benzoyl peroxide.

[0066] In some embodiments, the content of the component (C) is 5 to 25 parts by mass relative to 100 parts by mass of the component (A).

[0067] Further, the (C) includes: tetraethylene glycol dimethacrylate, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-isopropylimidazole, tetraphthalic anhydride, hexahydrophthalic anhydride, triethylenetetramine, dimethylaminopropylamine, diethylaminopropylamine, ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC, isopropylimidazole, tetraphthalic anhydride, hexahydrophthalic anhydride, triethylenetetramine, dimethylaminopropylamine, diethylaminopropylamine, ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC, DM-BI25X-F, 46DM℃, 46DMOIPP, 46DMOEP, DML-MBPC, DML-MB℃, DML-℃HP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-℃, dimethylol-Bis-C, dimethylol-Bis℃-P, DML-Bis℃-Z, DML-Bis℃HP-Z, At least one of DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, and DML-Bis25X-PCHP.

[0068] In some embodiments, the content of the component (D) is 0.1 to 1 part by mass relative to 100 parts by mass of the component (A).

[0069] It can be understood that according to the Clausius-Mo formula:

[0070]

[0071] In the formula, P m and V m Represent the molar polarizability and molar volume of the atomic groups in the polymer, respectively. By reducing the k value, the P m Or increase V m to achieve.

[0072] In some embodiments, the (E) includes: one or a combination of at least two of N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP) or N,N-dimethylformamide (DMF), tetrahydrofuran, m-cresol, γ-butyrolactone, tetramethylurea, dimethyl sulfoxide, hexamethylphosphoric acid triamide, and chloroform.

[0073] It can be understood that the ester-type photosensitive polyimide composite material provided in the above embodiments of the present application may further include (F) other components, including but not limited to polymerization inhibitors, copper surface adhesives, coupling agents, etc.

[0074] The ester-type photosensitive polyimide provided in this application reduces the dielectric constant by introducing fluorinated graphene quantum dots containing low-polarity fluorine atoms. Fluorine atoms have strong electronegativity, which can firmly fix electrons, thereby reducing polarizability. The small size and large specific surface area of ​​fluorinated graphene quantum dots make it easier to disperse evenly in the photosensitive polyimide matrix, thereby improving its overall performance and reducing the dielectric constant. The hydrophobicity of the fluorinated groups can also prevent the material from degrading due to water absorption. In addition, the molecular weight and grafting rate are controlled by adjusting the ratio of methacrylate groups, reaction temperature, and time, thereby achieving high sensitivity.

[0075] See also Figure 1 Another embodiment of the present application further provides a method for preparing an ester-type photosensitive polyimide composite material, including the following steps S110 to S130. The implementation method of each step is described in detail below.

[0076] Step S110: dissolving the fluorinated graphene quantum dots in the solvent, subjecting the solution to ultrasonic treatment for 30-90 minutes, and then adding the photoinitiator, the crosslinking agent and polyamic acid ester to obtain a fluorinated graphene quantum dot / polyamic acid ester composite solution.

[0077] In some embodiments, the fluorinated graphene quantum dots are prepared by the following method: placing a fluorinated carbon source in an organic solvent, then performing ultrasonic treatment, standing the solution, taking out the supernatant and centrifuging it, taking out the supernatant after centrifugation to remove the organic solvent, and finally drying to obtain the fluorinated graphene quantum dots.

[0078] In some embodiments, the carbon source includes at least one of fluorinated carbon fibers, fluorinated graphene, fluorinated carbon, and fluorinated carbon nanotubes.

[0079] In some embodiments, the organic solvent includes one or a combination of at least two of N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP) or N,N-dimethylformamide (DMF), tetrahydrofuran, m-cresol, γ-butyrolactone, tetramethylurea, dimethyl sulfoxide, hexamethylphosphoric acid triamide, and chloroform.

[0080] See also Figure 2 The preparation method of the polyamic acid ester provided in this embodiment includes the following steps S210 to S250, and the implementation method of each step is described in detail below.

[0081] Step S210: Under a nitrogen atmosphere, at a temperature of 40-45° C., dianhydride, hydroxyethyl methacrylate, pyridine and an organic solvent are mixed and reacted for 2-10 hours to obtain a mixed solution.

[0082] In some embodiments, the dianhydride includes pyromellitic dianhydride, maleic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3,4,4-diphenylsulfone tetracarboxylic dianhydride, 4,4'-phenylenedioxydiphthalic anhydride, hexafluorodianhydride, 1,2-ethylenebis[1,3-dihydro-1,3-dioxoisobenzofuran-5-carboxylate], bisphenol A dianhydride, glycerol bis(anhydrotrimellitate) acetate, At least one of 2,3,3',4'-biphenyltetracarboxylic dianhydride, p-phenylene-diphthalate dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 4,4'-(ethynyl-1,2-diyl)diphthalic anhydride, and 4,4'-thiodiphthalic anhydride.

[0083] It can be understood that before using the above-mentioned dianhydride, a step of treating the dianhydride is also included to remove impurities therein.

[0084] In some embodiments, the organic solvent includes one or a combination of at least two of N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP) or N,N-dimethylformamide (DMF), tetrahydrofuran, m-cresol, γ-butyrolactone, tetramethylurea, dimethyl sulfoxide, hexamethylphosphoric acid triamide, and chloroform.

[0085] Step S220: adding diamine to the mixed solution at 0° C. under a nitrogen atmosphere and stirring for 5-10 hours to perform a polycondensation reaction to form a hydroxyethyl methacrylate-terminated polyamic acid solution.

[0086] In some embodiments, the diamine includes 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, aminopropyl di-terminated polydimethylsiloxane, 3,5-diamino-1,2,4- Triazole, diaminopyridine, 2-(4-aminophenyl)-5-aminobenzimidazole, 2,2'-bis[4-(4-aminophenoxyphenyl)]propane, 2-amino-4-[(3,4-diaminophenyl)sulfonyl]aniline, 6,6'-bisamino-3,3'-methylenedibenzoic acid, 1-hydrogen-indazole-4,7-diamine, 7-nitro-1H-indazole-4-amine, 2,2'-diamino-4,4'-bithiazole, 3,6-diaminocarbazole, 2-(3,6-diamino-9H-carbazole-9-yl)acetic acid methyl ester, 2,5-diaminobenzothiazole, 2,6-Benzothiazolediamine, tert-butyl (6-amino-4-methylbenzo[D]thiazol-2-yl)carbamate, 4-methoxy-1,3-benzothiazole-2,6-diamine, benzoguanamine, 2,4-diamino-6-(2-fluorophenyl)-1,3,5-triazine, 2,4-diamino-6-(4-chlorophenyl)-1,3,5-triazine, 2,4-diamino-6-[4-(trifluoromethyl)phenyl]-1,3,5-triazine, 2,4-diamino-6-(3-fluorophenyl)-1,3,5-triazine, 2,4-diamino-6-[3-(trifluoromethyl)phenyl]-1,3,5- At least one of triazine, 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine, 2,4-diamino-6-(3,5-difluorophenyl)-1,3,5-triazine, 2,4-diamino-6-(4-bromophenyl)-1,3,5-triazine, 2,4-diamino-6-(4-methoxyphenyl)-1,3,5-triazine, 2,3-diaminophenolazine, methylguanamine, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-thiazine, 4,6-diaminopyrimidine, or various nitrogen-containing heterocyclic rings, siloxanes, thioethers and other diamines.

[0087] Step S230 : maintaining the temperature and atmosphere, adding trifluoroacetic anhydride to the polyamic acid solution and stirring for 0.5-3 hours to effect isoimidization.

[0088] Step S240 : Maintaining the nitrogen atmosphere, at a temperature of 50-55° C., adding hydroxyethyl methacrylate to the isoimidized polyamic acid solution and stirring for 8-12 hours to form a photosensitive polyimide precursor solution.

[0089] Step S250: dripping the photosensitive polyimide precursor solution into deionized water to remove unreacted substances, and then filtering and drying to obtain the polyamic acid ester.

[0090] It can be understood that polyamic acid ester can be obtained through the above steps S210 to S250, and its high sensitivity can be achieved by controlling the molecular weight and grafting rate by adjusting the ratio of methacrylate groups, reaction temperature, and time.

[0091] Step S120: applying the fluorinated graphene quantum dots / polyamic acid ester composite solution on the surface of the substrate, and then forming a pattern after exposure and development.

[0092] See also Figure 3 , which is a flow chart of the steps provided in this embodiment for coating the fluorinated graphene quantum dot / polyamic acid ester composite solution on the surface of the substrate and then forming a pattern after exposure and development, specifically including the following steps S310 to S340. The specific implementation method of each step is described in detail below.

[0093] Step S310: spin-coating the fluorinated graphene quantum dots / polyamic acid ester composite solution on the surface of the substrate.

[0094] Step S320: Soft-bake the spin-coated substrate at 100° C. for 3-10 minutes to remove part of the organic solvent, thereby obtaining a spin-coated film with a thickness of 2-5 μm.

[0095] Step S330: performing an exposure process on the substrate based on the spin-coated film.

[0096] Specifically, a mask with a pattern of 1:1 width ratio of the exposed portion and the unexposed portion per 1 μm in the range of 2 μm:2 μm to 30 μm:30 μm was used based on the spin-coated film. In addition, the exposure dose was 50 to 950 mJ / cm 2 The range is changed by 50mJ / cm 2 At the same time, reduced projection exposure is carried out to carry out the exposure process.

[0097] Step S340: developing the exposed substrate to form a line pattern.

[0098] It can be understood that through the above steps S310 to S340, the required pattern can be obtained.

[0099] Step S130: performing thermal imidization treatment on the pattern to obtain the ester-type photosensitive polyimide composite material.

[0100] In some embodiments, the step of performing thermal imidization treatment on the pattern to obtain the ester-type photosensitive polyimide composite material specifically includes:

[0101] Under a nitrogen atmosphere, the pattern was thermally imidized by a step-by-step heating method, wherein the step-by-step heating method was 100°C for 1 hour, 200°C for 1 hour, 300°C for 1 hour, and 350°C for 1 hour, with a heating rate of 2-10°C / minute. The pattern was then cooled to room temperature, and the pattern was peeled off from the substrate to obtain an ester-type photosensitive polyimide composite material with a low dielectric constant.

[0102] The preparation method of the ester-type photosensitive polyimide provided in the above-mentioned embodiments of this application reduces the dielectric constant by introducing fluorinated graphene quantum dots containing low-polarity fluorine atoms. Because fluorine atoms have strong electronegativity, they can firmly fix electrons, thereby reducing the polarizability. The small size and large specific surface area of ​​the fluorinated graphene quantum dots make it easier to evenly disperse in the photosensitive polyimide matrix, thereby improving its overall performance and reducing the dielectric constant. The fluorinated groups are hydrophobic, which can also prevent the material from degrading due to water absorption. In addition, the molecular weight and grafting rate are controlled by adjusting the ratio of methacrylate groups, reaction temperature, and time, thereby achieving high sensitivity.

[0103] The present application also provides a semiconductor device, comprising a copper wiring and an insulating layer disposed on the copper wiring, wherein the insulating layer comprises the ester-type photosensitive polyimide composite material.

[0104] The ester-type photosensitive polyimide provided in the present application reduces the dielectric constant of the photosensitive polyimide from about 3.8 to below 3.0 (2.4-2.9) by doping fluorinated graphene quantum dots into the photosensitive polyimide matrix, and significantly improves the hydrophobicity and mechanical properties. Its tensile strength increases from 84.5 MPa to 113.8 MPa, the elongation at break increases from 5.24% to 17.5%, the Young's modulus increases from 2.68 GPa to 3.02 GPa, and the water contact angle increases from 80.8° to 90.6°. Therefore, the photosensitive polyimide described in the present invention has excellent comprehensive performance and has good application prospects in advanced packaging technology.

[0105] The above technical solutions of the present application are described in detail below with reference to specific embodiments.

[0106] Example 1

[0107] (1) First, fluorinated carbon fibers were placed in 1000 ml of organic solvent, and then ultrasonicated for 6 hours using an ultrasonic disperser. After standing for 2 hours, the supernatant was centrifuged (3000 rpm, 10 minutes), the organic solvent was removed from the supernatant, and finally dried at 80°C to obtain fluorinated graphene quantum dots.

[0108] (2) Secondly, pre-treat the dianhydride and diamine to remove impurities therein. The diamine is treated in a vacuum oven at 60°C for 3 hours, and the dianhydride is treated in a vacuum oven at 160°C for 3 hours. Then, at 45°C, 1113 mg of pyromellitic dianhydride (the molar ratio of diamine to dianhydride is 0.9-1.05) is added to 10 ml of N-methylpyrrolidone. At the same time, 0.3089 g of hydroxyethyl methacrylate and 0.1869 g of pyridine are added to 10 ml of N-methylpyrrolidone and added to the dianhydride solution and stirred for 3 hours. After the dianhydride is completely dissolved, 1022 mg of 4,4'-diaminodiphenyl ether and 20 ml of N-methylpyrrolidone are added at 0°C and stirred continuously for 6 hours to obtain a hydroxyethyl methacrylate-terminated polyamic acid (PAA) solution. Subsequently, 5.94 g of trifluoroacetic anhydride was added dropwise to 30 ml of N-methylpyrrolidone and stirred rapidly for 1.5 hours to obtain a hydroxyethyl methacrylate-terminated polyisoimide solution. Subsequently, 7.8873 g of hydroxyethyl methacrylate was added to 5 ml of N-methylpyrrolidone and slowly added to the solution, stirring for 10 hours to obtain a polyamic acid ester solution. Finally, the polyamic acid ester solution was dripped dropwise into deionized water to remove unreacted impurities. The solution was then filtered and dried to obtain a polyamic acid resin. Then 21.4 mg of fluorinated graphene quantum dots was added to a brown bottle containing 8.35 g of N-methylpyrrolidone and ultrasonicated for 1 hour. Then, 428 mg of triethylene glycol dimethacrylate, 21.4 mg of OXE01, 21.4 mg of benzotriazole, 21.4 mg of 1,3,5-tris(4-tert-butyl 3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 4.28 g of polyamic acid ester were added thereto and shaken on a shaker for 24 hours to form a uniformly dispersed fluorinated graphene quantum dot / polyamic acid ester solution.

[0109] (3) Then, the fluorinated graphene quantum dots / polyamic acid ester composite solution is evenly spread on a clean silicon wafer by spin coating, and the pattern is obtained by the following steps:

[0110] 1. Soft bake the spin-coated wafer substrate on a hot plate at 100°C for 3-10 minutes to remove part of the organic solvent to obtain a spin-coated film with a thickness of 2-5 microns.

[0111] 2. Based on the spin-coated film, a mask with a pattern of 2μm:2μm to 30μm:30μm with a 1:1 ratio of exposed and unexposed areas per μm was used. Furthermore, the exposure step was performed while performing reduced projection exposure in increments of 50mJ / cm² within a range of 50 to 950mJ / cm².

[0112] 3. Develop the exposed wafer to form a line pattern.

[0113] (4) Finally, thermal imidization is carried out under a nitrogen atmosphere, mainly using a step-by-step heating method. The heating program is 100°C for 1 hour, 200°C for 1 hour, 300°C for 1 hour, and 350°C for 1 hour, with a heating rate of 2-10°C / minute. Then, the film is cooled to room temperature and the composite film is peeled off from the glass sheet to obtain fluorinated graphene quantum dots / photosensitive polyimide with high and low dielectric constants.

[0114] (5) The dielectric constant of the prepared composite film was tested using an Agilent 4294A impedance analyzer, and the lithographic morphology of the prepared composite film was observed using a 3D confocal microscope.

[0115] Example 2

[0116] The difference between the preparation method of this embodiment and that of the first embodiment is that the amount of fluorinated graphene quantum dots added in step (2) is replaced with 4.28 mg, and finally a photosensitive polyimide is obtained.

[0117] Example 3

[0118] The difference between the preparation method of this embodiment and that of the first embodiment is that the amount of fluorinated graphene quantum dots added in step (2) is replaced with 8.56 mg, and finally a photosensitive polyimide is obtained.

[0119] Example 4

[0120] The difference between the preparation method of this embodiment and that of the first embodiment is that the amount of fluorinated graphene quantum dots added in step (2) is replaced with 12.84 mg, and finally a photosensitive polyimide is obtained.

[0121] Example 5

[0122] The difference between the preparation method of this embodiment and that of the first embodiment is that the amount of fluorinated graphene quantum dots added in (2) is replaced with 32.1 mg, and finally a photosensitive polyimide is obtained.

[0123] Example 6

[0124] The preparation method of this embodiment differs from that of the first embodiment in that the amount of fluorinated graphene quantum dots added in step (2) is replaced with 42.8 mg, and finally a photosensitive polyimide is obtained.

[0125] Example 7

[0126] The difference between the preparation method of this embodiment and that of the first embodiment is that the amount of the photoinitiator added in step (2) is replaced with 42.8 mg, and finally a photosensitive polyimide is obtained.

[0127] Example 8

[0128] The difference between the preparation method of this embodiment and that of the first embodiment is that the amount of the photoinitiator added in step (2) is replaced with 85.6 mg, and finally a photosensitive polyimide is obtained.

[0129] Example 9

[0130] The difference between the preparation method of this embodiment and that of the first embodiment is that the amount of the photoinitiator added in step (2) is replaced with 128.4 mg, and finally a photosensitive polyimide is obtained.

[0131] Example 10

[0132] The difference between the preparation method of this embodiment and that of the first embodiment is that the amount of the photoinitiator added in step (2) is replaced with 171.2 mg, and finally a photosensitive polyimide is obtained.

[0133] Example 11

[0134] The difference between the preparation method of this embodiment and that of the first embodiment is that the amount of the photoinitiator added in step (2) is replaced with 214 mg, and finally a photosensitive polyimide is obtained.

[0135] Example 12

[0136] The difference between the preparation method of this embodiment and that of the first embodiment is that the amount of the cross-linking agent added in step (2) is replaced with 214 mg, and finally a photosensitive polyimide is obtained.

[0137] Example 13

[0138] The difference between the preparation method of this embodiment and that of the first embodiment is that the amount of the cross-linking agent added in step (2) is replaced with 535 mg, and finally a photosensitive polyimide is obtained.

[0139] Example 14

[0140] The difference between the preparation method of this embodiment and that of the first embodiment is that the amount of the cross-linking agent added in step (2) is replaced with 642 mg, and finally a photosensitive polyimide is obtained.

[0141] Example 15

[0142] The difference between the preparation method of this embodiment and that of the first embodiment is that the amount of the cross-linking agent added in step (2) is replaced with 856 mg, and finally a photosensitive polyimide is obtained.

[0143] Example 16

[0144] The difference between the preparation method of this embodiment and that of the first embodiment is that the amount of the cross-linking agent added in step (2) is replaced with 1070 mg, and finally a photosensitive polyimide is obtained.

[0145] Comparative Example 1

[0146] The difference between the preparation method of this comparative example and that of Example 1 is that the prepared fluorinated graphene quantum dots are not added in step (2), and finally photosensitive polyimide is obtained.

[0147] The properties of the ester-type photosensitive polyimide composite material prepared in the above embodiment are shown in the table below:

[0148] Implementation Example Dielectric constant Resolution Implementation Example Dielectric constant Resolution Example 1 2.93 6μm Example 9 2.93 3μm Example 2 3.41 6μm Example 10 2.93 3μm Example 3 3.22 6μm Example 11 2.93 3μm Example 4 3.06 6μm Example 12 2.93 8μm Example 5 2.74 6μm Example 13 2.93 5μm Example 6 3.12 6μm Example 14 2.93 4μm Example 7 2.93 5μm Example 15 2.93 3μm Example 8 2.93 4μm Example 16 2.93 3μm Comparative Example 1 3.8 6μm

[0149] In order to analyze the effect of ultrasonic dispersion on the intrinsic fluorine content of fluorinated graphene quantum dots, XPS analysis was performed on the fluorinated graphene quantum dots prepared in Example 1. The results are as follows: Figure 4 As shown in FIG, it can be clearly seen that ultrasonic treatment of the fluorinated carbon source by using an ultrasonic disperser does not affect the original fluorine content of the fluorinated carbon source. In order to further observe the morphological characteristics of the prepared fluorinated graphene quantum dots, TEM analysis was performed on the fluorinated graphene quantum dots prepared in Example 1, and the results are shown in FIG. Figure 5 As shown in the figure, it can be clearly observed that after ultrasonic treatment of the fluorinated carbon source using an ultrasonic disperser, the size of the prepared fluorinated graphene quantum dots is uniform and below 10 nm, which is conducive to the dispersion of the fluorinated graphene quantum dots in the photosensitive polyimide matrix. By comparing the dielectric constants of the pure photosensitive polyimide film and the composite film with fluorinated graphene quantum dots added in Example 1, the results show that Figure 6 As shown in the figure, it can be clearly seen that the introduction of fluorinated graphene quantum dots can effectively reduce the dielectric constant of the photosensitive polyimide film. At 1 MHz, the dielectric constant of the photosensitive polyimide is successfully reduced from about 3.8 to below 3.0. By comparing the mechanical properties of the pure photosensitive polyimide film (tensile strength of 84.5 MPa, elongation at break of 5.24%, and Young's modulus of 2.68 GPa) with the composite film with fluorinated graphene quantum dots added in Example 1, the results are shown in Figure 2. Figure 7 As shown in the figure, it can be clearly seen that the introduction of fluorinated graphene quantum dots can effectively enhance the mechanical properties of the photosensitive polyimide film, with the tensile strength increased to 113.8 MPa, the elongation at break increased to 17.5%, and the Young's modulus increased to 3.02 GPa. Figure 8 As shown, the photosensitive polyimide prepared in Example 1 exhibits high sensitivity, and its resolution can reach about 3 microns.

[0150] It can be understood that the various technical features of the above-mentioned embodiments can be arbitrarily combined. In order to make the description concise, not all possible combinations of the various technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification. The above are only preferred embodiments of the present application, and only the technical principles of the present application are specifically described. These descriptions are only for explaining the principles of the present application and cannot be interpreted as limiting the scope of protection of the present application in any way. Based on the explanation here, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application, and other specific implementation methods of the present application that can be associated with the technical personnel in this field without creative work, should be included in the scope of protection of the present application.

Claims

1. An ester-type photosensitive polyimide composite material, characterized in that: Includes the following ingredients: (A) component: polyamic acid ester; (B) ingredient: photoinitiator; (C) component: a cross-linking agent; (D) ingredient: fluorinated graphene quantum dots; and (E) ingredient: solvent; Said (B) is OXE01; The (C) is tetraethylene glycol dimethacrylate; The content of the component (B) is 0.5 to 5 parts by mass relative to 100 parts by mass of the component (A); The content of the component (C) is 5 to 25 parts by mass relative to 100 parts by mass of the component (A); The content of the component (D) is 0.1 to 1 part by mass relative to 100 parts by mass of the component (A); The preparation method of the ester-type photosensitive polyimide composite material comprises the following steps: dissolving fluorinated graphene quantum dots in the solvent, performing ultrasonic treatment for 30-90 minutes, and then adding the photoinitiator, the crosslinking agent, and polyamic acid ester to obtain a fluorinated graphene quantum dot / polyamic acid ester composite solution; Applying the fluorinated graphene quantum dots / polyamic acid ester composite solution on the surface of a substrate, and then exposing and developing the solution to form a pattern; performing thermal imidization treatment on the pattern to obtain the ester-type photosensitive polyimide composite material; The fluorinated graphene quantum dots are prepared by the following method: placing a fluorinated carbon source in an organic solvent, performing ultrasonic treatment, allowing the solution to stand for centrifugation, removing the organic solvent from the supernatant, and drying the solution to obtain fluorinated graphene quantum dots; The carbon source is fluorinated carbon fiber; The polyamic acid ester is prepared by the following method: Under a nitrogen atmosphere, at a temperature of 40-45° C., mixing dianhydride, hydroxyethyl methacrylate, pyridine and an organic solvent for reaction for 2-10 hours to obtain a mixed solution; In a nitrogen atmosphere at 0-25° C., adding diamine to the mixed solution and stirring for 5-10 hours to perform a polycondensation reaction to form a hydroxyethyl methacrylate-terminated polyamic acid solution; While maintaining the temperature and atmosphere, trifluoroacetic anhydride is added to the polyamic acid solution and stirred for 0.5-3 hours to effect isoimidization; Maintaining the mixture under a nitrogen atmosphere, at a temperature of 50-55° C., adding hydroxyethyl methacrylate to the isoimidized polyamic acid solution and stirring for 8-12 hours to form a photosensitive polyimide precursor solution; The photosensitive polyimide precursor solution is dropped into deionized water to remove unreacted substances, and then filtered and dried to obtain the polyamic acid ester; The dianhydride is pyromellitic dianhydride; The diamine is 4,4'-diaminodiphenyl ether 4,4'-diaminodiphenyl ether; The step of performing thermal imidization treatment on the pattern to obtain the ester-type photosensitive polyimide composite material specifically includes: Under a nitrogen atmosphere, the pattern is thermally imidized by a step-by-step heating method, wherein the step-by-step heating method is as follows: keeping the temperature at 100°C for 0.5-1.5 hours, keeping the temperature at 200°C for 0.5-1.5 hours, keeping the temperature at 300°C for 0.5-1.5 hours, and keeping the temperature at 350°C for 0.5-1.5 hours, with a heating rate of 2-10°C / minute. The pattern is then cooled to room temperature, and the pattern is peeled off from the substrate to obtain an ester-type photosensitive polyimide composite material with a low dielectric constant.

2. The ester-type photosensitive polyimide composite material according to claim 1, wherein: The (E) includes: one or a combination of at least two of N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP) or N,N-dimethylformamide (DMF), tetrahydrofuran, m-cresol, γ-butyrolactone, tetramethylurea, dimethyl sulfoxide, hexamethylphosphoric acid triamide, and chloroform.

3. A method for preparing the ester-type photosensitive polyimide composite material according to claim 1, characterized in that: The steps include: dissolving fluorinated graphene quantum dots in the solvent, performing ultrasonic treatment for 30-90 minutes, and then adding the photoinitiator, the crosslinking agent, and polyamic acid ester to obtain a fluorinated graphene quantum dot / polyamic acid ester composite solution; Applying the fluorinated graphene quantum dots / polyamic acid ester composite solution on the surface of a substrate, and then exposing and developing the solution to form a pattern; performing thermal imidization treatment on the pattern to obtain the ester-type photosensitive polyimide composite material; The fluorinated graphene quantum dots are prepared by the following method: placing a fluorinated carbon source in an organic solvent, performing ultrasonic treatment, allowing the solution to stand for centrifugation, removing the organic solvent from the supernatant, and drying the solution to obtain fluorinated graphene quantum dots; The carbon source is fluorinated carbon fiber; The polyamic acid ester is prepared by the following method: Under a nitrogen atmosphere, at a temperature of 40-45° C., mixing dianhydride, hydroxyethyl methacrylate, pyridine and an organic solvent for reaction for 2-10 hours to obtain a mixed solution; In a nitrogen atmosphere at 0-25° C., adding diamine to the mixed solution and stirring for 5-10 hours to perform a polycondensation reaction to form a hydroxyethyl methacrylate-terminated polyamic acid solution; While maintaining the temperature and atmosphere, trifluoroacetic anhydride is added to the polyamic acid solution and stirred for 0.5-3 hours to effect isoimidization; Maintaining the mixture under a nitrogen atmosphere, at a temperature of 50-55° C., adding hydroxyethyl methacrylate to the isoimidized polyamic acid solution and stirring for 8-12 hours to form a photosensitive polyimide precursor solution; The photosensitive polyimide precursor solution is dropped into deionized water to remove unreacted substances, and then filtered and dried to obtain the polyamic acid ester; The dianhydride is pyromellitic dianhydride; The diamine is 4,4'-diaminodiphenyl ether 4,4'-diaminodiphenyl ether; The step of performing thermal imidization treatment on the pattern to obtain the ester-type photosensitive polyimide composite material specifically includes: Under a nitrogen atmosphere, the pattern is thermally imidized by a step-by-step heating method, wherein the step-by-step heating method is as follows: keeping the temperature at 100°C for 0.5-1.5 hours, keeping the temperature at 200°C for 0.5-1.5 hours, keeping the temperature at 300°C for 0.5-1.5 hours, and keeping the temperature at 350°C for 0.5-1.5 hours, with a heating rate of 2-10°C / minute. The pattern is then cooled to room temperature, and the pattern is peeled off from the substrate to obtain an ester-type photosensitive polyimide composite material with a low dielectric constant.

4. The method for preparing the ester-type photosensitive polyimide composite material according to claim 3, wherein: The organic solvent includes one or a combination of at least two of N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP) or N,N-dimethylformamide (DMF), tetrahydrofuran, m-cresol, γ-butyrolactone, tetramethylurea, dimethyl sulfoxide, hexamethylphosphoric acid triamide, and chloroform.

5. The method for preparing the ester-type photosensitive polyimide composite material according to claim 3, wherein: The step of applying the fluorinated graphene quantum dots / polyamic acid ester composite solution on the surface of the substrate and then exposing and developing the solution to form a pattern specifically includes the following steps: Spin coating the fluorinated graphene quantum dots / polyamic acid ester composite solution on the surface of the substrate; The spin-coated substrate is soft-baked at 80-120° C. for 3-10 minutes to remove part of the organic solvent to obtain a spin-coated film with a thickness of 2-5 μm; performing an exposure process on the substrate based on the spin-coated film; The exposed substrate is developed to form a line pattern.

6. A semiconductor device, characterized in that: The invention comprises a copper wiring and an insulating layer provided on the copper wiring, wherein the insulating layer comprises the ester-type photosensitive polyimide composite material according to any one of claims 1-2 or the ester-type photosensitive polyimide composite material prepared by the preparation method according to any one of claims 3 to 5.

Images