A positive photosensitive polybenzoxazole resin composition, preparation method and application thereof

Abstract

The invention discloses a positive photosensitive polybenzoxazole resin composition, a preparation method and an application thereof. The composition comprises the following components in parts by weight: 100 parts by weight of an aromatic silicon-containing polybenzoxazole precursor polymer, 1-50 parts by weight of a photosensitizer, 80-800 parts by weight of a solvent and an additive. The positive photosensitive polybenzoxazole resin composition is applied through coating, pre-baking, exposure, development and thermal curing. The aromatic silicon-containing polybenzoxazole precursor polymer is obtained by polycondensing an aromatic silicon-containing diacid and an acyl halide thereof with a hydroxyl-containing diamine by a known method. The introduction of the aromatic silicon-containing structure can improve the flexibility of the polymer molecular chain and reduce the rigidity. The silicon-oxygen structure has good affinity for substrates such as silicon, glass and ITO, thereby improving the bonding performance between the polybenzoxazole film and the substrate, enabling the polybenzoxazole film to withstand the high temperature of the thermal cyclization process and complex operating environments.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a positive photosensitive polybenzoxazole resin composition, a preparation method and applications thereof. Background Art

[0002] It is well known that high-temperature-resistant polymers are crucial materials in microelectronic applications, with polyimides and polybenzoxazoles being the most representative. These polymers, thanks to their excellent electrical insulation, high-temperature resistance, chemical resistance, and mechanical properties, are widely used in the semiconductor field, such as for interlayer insulation and surface passivation in microelectronic chips, and as packaging materials for electronic and electrical components. These polymers typically require conventional photoresists for patterning, a complex process that is particularly costly and has low yield rates, especially for structures such as multi-layer metal interconnects. Furthermore, the need to remove the used photoresist often compromises the overall performance of the final film. By adding suitable compound components, these polymers and their precursors can be made into photosensitive resin compositions. The resin composition is coated on a substrate, typically silicon, and patterning can be achieved using known methods, such as developing in an alkaline aqueous solution after electromagnetic wave irradiation, significantly shortening the process flow and greatly improving production efficiency.

[0003] In recent years, photosensitive polybenzoxazole compositions have gained attention due to their low water absorption and dielectric constant, and their ability to effectively prevent atomic migration within device layers as a protective layer. However, the thermally cyclized benzoxazole molecules exhibit a rod-like structure and high rigidity. While this provides excellent mechanical properties and thermal stability, it also leaves significant residual stress at the interface due to film shrinkage, reducing interaction with the substrate. Consequently, the cured film, as a component of semiconductor devices, exhibits poor adhesion to the substrate, potentially leading to device failure and posing a significant risk to the stable operation of electronic components.

[0004] In this regard, through the exploration and experimentation of researchers, it was found that silicon-containing structures can be introduced in different ways to form various chemical bonds with the substrate to enhance adhesion to the substrate. For example, protective grafting of side chains onto the main chain of the polymer resin, and introduction of silane-containing groups into the side chains; or introduction of silicon-containing structures into both ends of the main chain of the linear molecule in the form of end caps; there are also reports that adding a certain amount of one or several silane coupling agents containing special structures or specific functional groups to the resin composition can enhance adhesion. However, different problems have also been found in practice. For example, if a side chain is introduced, the side chain will fall off during the later cyclization process, causing the film to lose its connection with the substrate; if it is introduced in the form of end caps or small molecules as additives, only a very small part of the structure has good tolerance, and most of the structures will decompose due to the breakage of chemical bonds caused by high temperature during the film curing process or working in a complex environment, and the final result is a reduction in adhesion to the substrate. Another problem is that the types and amounts of silicon-containing small molecules added as additives are limited. Various spontaneous reactions such as self-condensation due to long-term water vapor infiltration and other factors must be prevented during storage, as this will cause a significant change in the viscosity of the resin composition itself and a significant reduction in photosensitivity, resulting in a significant reduction in product yield under normal production process flow. Summary of the Invention

[0005] The object of the present invention is to provide a positive photosensitive polybenzoxazole resin composition, a preparation method and application thereof, so as to solve the problems raised in the above background technology.

[0006] To achieve the above object, the present invention provides the following technical solution: a positive photosensitive polybenzoxazole resin composition, comprising the following components in parts by weight: 100 parts by weight of an aromatic silicon-containing polybenzoxazole precursor polymer, 1-50 parts by weight of a photosensitizer, 80-800 parts by weight of a solvent, and additives;

[0007] The additive is selected from one or a combination of two or more of a photosensitive auxiliary agent, a thermal crosslinking agent and an adhesion promoter. The addition amount of the photosensitive auxiliary agent is 1-10 parts by weight, the addition amount of the thermal crosslinking agent is 5-20 parts by weight, and the addition amount of the adhesion promoter is 0.01-0.5 parts by weight.

[0008] Preferably, the general structure of the aromatic silicon-containing polybenzoxazole precursor polymer is represented by general formula (i), which is as follows:

[0009]

[0010] Wherein, R1 is a divalent organic group, serving as a residue of a dicarboxylic acid, and R2 is a tetravalent organic group, serving as a residue of a dihydroxydiamine; n is a positive integer, and the selected range is 20-60;

[0011] The R1 of the dicarboxylic acid residue has an aromatic silicon-containing structure, and its general structural formula (ii) is shown as follows:

[0012]

[0013] in,

[0014]

[0015] Preferably, the photosensitizer is a mixture of one or more of tris(1,2,5-diazonaphthoquinonesulfonic acid phenyl ester)methane, tris(1,2,5-diazonaphthoquinonesulfonic acid phenyl ester)-1-ethyl-4-isopropylbenzene, 2,3,4-tris(1,2,5-diazonaphthoquinonesulfonic acid ester)benzophenone and 2,3,4,4'-tetrakis(1,2,5-diazonaphthoquinonesulfonic acid ester)benzophenone.

[0016] Preferably, the solvent is selected from one or a mixture of two or more of N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, propylene glycol methyl ether, cyclopentanone, cyclohexanone, methyl ethyl ketone, γ-butyrolactone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, butyl acetate, and propylene glycol methyl ether acetate.

[0017] Preferably, the photosensitive auxiliary agent is a photoacid generator, and the photoacid generator is an ionic acid generator, a non-ionic acid generator, or a mixture of the two;

[0018] The ionic acid generator can be selected from one of 4,4'-di-tert-butylphenyl iodide trifluorosulfonate, perfluorobutylsulfonic acid triphenylsulfonium salt, 4,4'-ditolyl iodide hexafluorophosphate, 9,10-dimethoxy-2-anthracenesulfonic acid diphenyl iodide salt or a mixture of two or more thereof;

[0019] The nonionic acid generator is a compound having the following structure:

[0020]

[0021] Preferably, the photosensitive auxiliary agent is a thermal crosslinking agent, and the thermal crosslinking agent can be a compound having the following structure:

[0022]

[0023] Preferably, the photosensitive auxiliary agent is an adhesion promoter, the adhesion promoter is a silane coupling agent containing a phenyl silicon structure with excellent heat resistance, and the silane coupling agent is selected from one of m-phenylene trimethoxysilane, m-phenylene triethoxysilane, p-phenylene triethoxysilane, p-phenylene trimethoxysilane, p-isopropenylphenyl triethoxysilane, and p-isopropenylphenyl trimethoxysilane, or a mixture of two or more thereof.

[0024] Another object of the present invention is to disclose a method for preparing a positive photosensitive polybenzoxazole resin composition, comprising the following preparation steps: adding the above-mentioned solvent to a glass or stainless steel container in a yellow light chamber, adding the synthesized aromatic silicon-containing polybenzoxazole precursor polymer, and stirring to completely dissolve it; adding the above-mentioned photosensitizer and the above-mentioned additives, stirring and dissolving to obtain a homogeneous resin composition solution; and finally filtering the composition using a filter with a pore size of 0.1μm-5μm to remove foreign matter to obtain a positive photosensitive polybenzoxazole resin composition.

[0025] Another object of the present invention is to disclose an application of a positive photosensitive polybenzoxazole resin composition. The application of the positive photosensitive polybenzoxazole resin composition is completed through the steps of coating, pre-baking, exposure, development and thermal curing. The specific steps are as follows:

[0026] (1) Coating: coating the positive photosensitive polybenzoxazole resin composition on a silicon substrate;

[0027] (2) Pre-baking: heating and drying the silicon substrate coated with the positive photosensitive polybenzoxazole resin composition to remove the solvent and obtain a positive photosensitive resin film;

[0028] (3) Exposure: Exposure is performed by irradiating ultraviolet light through a photomask having a desired pattern on the positive photosensitive resin film;

[0029] (4) Development: After exposure, a developer is used to remove the exposed portion to obtain the desired pattern.

[0030] (5) Thermal curing: The developed film is further heated to cure it on the substrate to obtain a positive photosensitive polybenzoxazole resin layer with the desired pattern.

[0031] Preferably, the developer in step (4) is selected from one of an aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] (1) The aromatic silicon-containing polybenzoxazole precursor polymer of the present invention is obtained by polycondensing an aromatic silicon-containing diacid and its acyl halide with a hydroxyl-containing diamine by a known method. The introduction of the aromatic silicon-containing structure can improve the flexibility of the polymer molecular chain and reduce the rigidity. The silicon-oxygen structure has a good affinity for substrates such as silicon, glass, and ITO, thereby improving the bonding performance between the polybenzoxazole film and the substrate, allowing it to withstand the high temperature of the thermal cyclization process and the complex use environment. At the same time, the silicon-containing structure can further reduce hygroscopicity and internal stress, obtain a low dielectric constant and high atomic oxygen resistance, and improve the reliability of microelectronic devices.

[0034] (2) In terms of the selection of additives, the present invention uses a suitable photosensitive auxiliary agent to effectively reduce the energy required for exposure of the resin composition in combination with the photosensitive agent, thereby improving sensitivity and making it highly sensitive. The use of a suitable thermal crosslinking agent can improve the alkaline water corrosion resistance of the unexposed portion of the resin film, help improve the film retention rate, obtain high-resolution graphics, and also improve the mechanical properties of the film after thermal cyclization. Not adding or selectively adding only a small amount of a high-temperature resistant phenyl silicon structure adhesion promoter can prevent the self-condensation of high-content siloxane during storage, thereby improving storage stability. DETAILED DESCRIPTION

[0035] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0036] The evaluation method for the positive photosensitive polybenzoxazole resin composition is as follows:

[0037] (1) Viscosity test

[0038] 10 ml of the resin composition glue was placed in the sample cell of a rotational viscometer (BROOKFIELD DV2T RV), and a suitable measuring range was selected and the temperature was controlled at 25°C ± 0.1°C to perform a viscosity test.

[0039] (2) Photosensitivity test

[0040] A positive photosensitive polybenzoxazole resin composition was coated on a 6-inch silicon wafer and then baked at 120°C for 3 minutes using a hot plate to obtain a photosensitive resin film. The film thickness was measured using a Filmetrics FC20 (produced by KLA, USA) film thickness meter, and the measurement result was used as the pre-baked film thickness. The silicon wafer covered with the dry film was placed in a photolithography machine (URE-2000 / B, produced by the Institute of Optoelectronics Technology, Chinese Academy of Sciences), a mask was placed on it, and 365nm light (i-line) was selected for exposure. The exposed silicon wafer was placed in a developer (2.38% TMAH aqueous solution: isopropyl alcohol = 95:5 (volume ratio)) for 90 seconds, and the temperature was controlled at 23°C ± 1°C. After development, it was rinsed with ultrapure water and dried. The film thickness was measured, and the measurement result was used as the developed film thickness. The minimum exposure energy required for the film to be fully developed was used as the sensitivity.

[0041] The film retention rate of the photosensitive resin film is calculated using the following formula:

[0042] Film retention rate (%) = (film thickness after development / film thickness after pre-baking) × 100%.

[0043] (3) Adhesion peeling test between cured film and substrate

[0044] The adhesive solution was applied to a 6-inch silicon wafer and then baked on a hot plate at 120°C for 3 minutes to obtain a photosensitive resin film. The prepared photosensitive resin film was then placed on a hot plate for a step-by-step heat treatment. The film was first heat treated at 90°C for 60 minutes, followed by heat treatment at 150°C for 60 minutes, heat treatment at 240°C for 60 minutes, and finally heat treatment at 320°C for 60 minutes to obtain a cured film.

[0045] The cured film was cut into a checkerboard pattern of 10 rows and 10 columns at 2 mm intervals. A peel test was performed using a special transparent 3M tape in accordance with the national standard GB / T 9286-1998 (cross-cut test for paint and varnish films). The number of squares peeled off was recorded.

[0046] The cured film with the grid pattern was placed in a high-pressure accelerated aging test chamber (Xiamen Easy Instrument Technology ST-PCT40) and subjected to a 100-hour PCT test (conditions: 121°C, 2 atmospheres of saturated steam). After the PCT test, a peel test was performed using the same tape, and the results were recorded. A peel test of less than 10 pieces removed was considered good, and a peel test of 10 or more pieces was considered poor.

[0047] (4) Storage stability test

[0048] After storage for one week in a yellow light room (23°C, 45% RH), the viscosity and photosensitivity were tested. A change of 5% or less was considered good, and a change of 5% or more was considered poor. Adhesion to the substrate after storage was evaluated using the same tape peel test criteria.

[0049] Synthesis example 1

[0050] In a 500 ml flask equipped with a stirrer and thermometer, place 22.47 g (60 mmol) of 1,3-bis(4-carboxyphenyl)-1,1,3,3-tetramethyldisiloxane (SiBDA) and 90 g of N-methylpyrrolidone. Cool the flask to 5°C, then add 23.9 g (120 mmol) of thionyl chloride dropwise. Allow the mixture to react for 30 minutes to obtain a solution of the corresponding silicon-containing aromatic diacid chloride.

[0051] In a 500 ml flask equipped with a stirrer and a thermometer, place 90 g of N-methylpyrrolidone. Add 20.14 g (55 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 1.09 g (10 mmol) of p-aminophenol and stir to dissolve. Then add 9.48 g (120 mmol) of pyridine. Cool the flask to 5°C and then add the above-mentioned silicon-containing aromatic dichloride solution dropwise, maintaining the temperature at 0-5°C for 30 minutes, and then continue stirring at room temperature for 10 hours. The reaction solution is poured into 3 L of 10 wt% methanol aqueous solution to precipitate a polymer to obtain a white precipitate. After filtering, wash three times with deionized water, place in a vacuum oven, and dry under reduced pressure at 60°C for 72 hours to obtain polybenzoxazole precursor polymer P1.

[0052] Synthesis example 2

[0053] In a 500 mL flask equipped with a stirrer and thermometer, place 20.60 g (55 mmol) of 1,3-bis(4-carboxyphenyl)-1,1,3,3-tetramethyldisiloxane (SiBDA) and 90 g of N-methylpyrrolidone. Cool the flask to 5°C, then add 21.91 g (110 mmol) of thionyl chloride dropwise. Allow the mixture to react for 30 minutes to obtain a solution of the corresponding silicon-containing aromatic diacid chloride.

[0054] In a 500 ml flask equipped with a stirrer and a thermometer, place 90 g of N-methylpyrrolidone and 15.50 g (60 mmol) of bis(3-amino-4-hydroxyphenyl)propane and stir to dissolve. Subsequently, add 8.69 g (110 mmol) of pyridine. Cool the flask to 5°C, then add the above-mentioned silicon-containing aromatic dichloride solution dropwise, maintaining the temperature at 0-5°C, and continue stirring at room temperature for 10 hours. Add 1.64 g (10 mmol) of 4-hydroxyphthalic anhydride, continue stirring for 3 hours after dissolution. Pour the reaction solution into 3 L of 10 wt% methanol aqueous solution, precipitate the polymer to obtain a white precipitate, filter, wash three times with deionized water, place in a vacuum oven, and dry under reduced pressure at 60°C for 72 hours to obtain polybenzoxazole precursor polymer P2.

[0055] Synthesis example 3

[0056] The rest of the preparation process was the same as that of Synthesis Example 2, except that 15.50 g (60 mmol) of bis(3-amino-4-hydroxyphenyl)propane was replaced by 12.97 g (60 mmol) of 3,3'-diamino-4,4'-dihydroxybiphenyl and 1.64 g (10 mmol) of 4-hydroxyphthalic anhydride was replaced by 1.64 g (10 mmol) of nadic anhydride, to finally obtain a polybenzoxazole precursor polymer P3.

[0057] Synthesis example 4

[0058] In a 500 mL flask equipped with a stirrer and thermometer, place 23.90 g (55 mmol) of 1,3-bis(4-carboxyphenoxymethyl)-1,1,3,3-tetramethyldisiloxane (SiMBDA) and 90 g of cyclopentanone. Cool the flask to 5°C, then add 21.91 g (110 mmol) of thionyl chloride dropwise. Allow the mixture to react for 30 minutes to obtain a solution of the corresponding silicon-containing aromatic diacid chloride.

[0059] In a 500 ml flask equipped with a stirrer and a thermometer, place 90 g of cyclopentanone and 21.98 g (60 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane and stir to dissolve. Subsequently, add 8.69 g (110 mmol) of pyridine. Cool the flask to 5°C, then add the above-mentioned silicon-containing aromatic dichloride solution dropwise, maintaining the temperature at 0-5°C for 30 minutes, and then continue stirring at room temperature for 10 hours. Add 1.64 g (10 mmol) of 4-hydroxyphthalic anhydride, continue stirring for 3 hours after dissolution. Pour the reaction solution into 3 L of 10 wt% methanol aqueous solution, precipitate the polymer to obtain a white precipitate, filter, wash three times with deionized water, place in a vacuum oven, and dry under reduced pressure at 60°C for 72 hours to obtain polybenzoxazole precursor polymer P4.

[0060] Synthesis example 5

[0061] The rest of the preparation was the same as that of Synthesis Example 4, except that 21.98 g (60 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane was changed to 22.83 g (60 mmol) of 9,9-bis(3-amino-4-hydroxyphenyl)fluorene and 1.64 g (10 mmol) of 4-hydroxyphthalic anhydride was changed to 2.48 g (10 mmol) of 4-phenylethynylphthalic anhydride, and finally a polybenzoxazole precursor polymer P5 was obtained.

[0062] Synthesis example 6

[0063] The rest of the process was the same as that of Synthesis Example 4, except that 21.98 g (60 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane was replaced by 13.93 g (60 mmol) of 3,3'-diamino-4,4'-dihydroxydiphenyl ether and 1.64 g (10 mmol) of 4-hydroxyphthalic anhydride was replaced by 1.64 g (10 mmol) of nadic anhydride, and finally a polybenzoxazole precursor polymer P6 was obtained.

[0064] Synthesis Example 7

[0065] In a 500 mL flask equipped with a stirrer and thermometer, place 34.26 g (55 mmol) of 1,3-bis(4-carboxyphenyl)-1,1,3,3-tetraphenyldisiloxane (SiHBDA) and 90 g of diethylene glycol dimethyl ether. Cool the flask to 5°C, then add 21.91 g (110 mmol) of thionyl chloride dropwise. Allow the mixture to react for 30 minutes to obtain a solution of the corresponding silicon-containing aromatic diacid chloride.

[0066] In a 500 ml flask equipped with a stirrer and a thermometer, place 90 g of diethylene glycol dimethyl ether and 15.50 g (60 mmol) of bis(3-amino-4-hydroxyphenyl)propane and stir to dissolve. Subsequently, add 8.69 g (110 mmol) of pyridine. Cool the flask to 5°C, then add the above-mentioned silicon-containing aromatic dichloride solution dropwise, maintain the temperature at 0-5°C, add dropwise for 30 minutes, and then continue stirring at room temperature for 10 hours. Add 2.48 g (10 mmol) of 4-phenylethynylphthalic anhydride, continue stirring for 3 hours after dissolution. Pour the reaction solution into 3 L of 10 wt% methanol aqueous solution, precipitate the polymer to obtain a white precipitate, filter it, wash it three times with deionized water, place it in a vacuum oven, and dry it under reduced pressure at 60°C for 72 hours to obtain the polybenzoxazole precursor polymer P7.

[0067] Synthesis example 8

[0068] The rest of the preparation was the same as that of Synthesis Example 7, except that 15.50 g (60 mmol) of bis(3-amino-4-hydroxyphenyl)propane was changed to 21.98 g (60 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.48 g (10 mmol) of 4-phenylethynylphthalic anhydride was changed to 1.64 g (10 mmol) of nadic anhydride, and finally a polybenzoxazole precursor polymer P8 was obtained.

[0069] Synthesis example 9

[0070] The rest of the preparation process was the same as that of Synthesis Example 7, except that 15.50 g (60 mmol) of bis(3-amino-4-hydroxyphenyl)propane was replaced by 13.93 g (60 mmol) of 3,3'-diamino-4,4'-dihydroxydiphenyl ether and 2.48 g (10 mmol) of 4-phenylethynylphthalic anhydride was replaced by 1.64 g (10 mmol) of 4-hydroxyphthalic anhydride, to finally obtain polybenzoxazole precursor polymer P9.

[0071] Synthesis example 10

[0072] In a 500 ml flask equipped with a stirrer and thermometer, place 180 g of γ-butyl ester. Add 11.89 g (55 mmol) of 3,3'-diamino-4,4'-dihydroxybiphenyl and stir to dissolve. Then add 8.69 g (110 mmol) of pyridine. Cool the flask to 5°C, then add a total of 11.17 g (55 mmol) of isophthaloyl chloride in batches, maintaining the temperature at 0-5°C, add dropwise for 30 minutes, and then continue stirring at room temperature for 10 hours. Pour the reaction solution into 3 L of 10 wt% methanol aqueous solution, precipitate the polymer to obtain a white precipitate, filter it, wash it three times with deionized water, place it in a vacuum oven, and dry it under reduced pressure at 60°C for 72 hours to obtain the polybenzoxazole precursor polymer P10.

[0073] Synthesis Example 11

[0074] The rest of the process was the same as that of Synthesis Example 10, except that 11.17 g (55 mmol) of isophthaloyl dichloride was replaced with 16.23 g (55 mmol) of diphenyl ether dichloride, to finally obtain polybenzoxazole precursor polymer P11.

[0075] Synthesis example 12

[0076] The rest of the process was the same as that of Synthesis Example 10, except that 11.17 g (55 mmol) of isophthaloyl dichloride was replaced with 15.35 g (55 mmol) of 4,4'-biphenylacetyl chloride, to finally obtain polybenzoxazole precursor polymer P12.

[0077] Example 1

[0078] 40 parts by weight of polybenzoxazole precursor resin P1 was added to 60 parts by weight of γ-butyrolactone and stirred at room temperature for 2 hours to form a homogeneous solution. In a dark room equipped with a yellow light, 10 parts by weight of tris(1,2,5-diazonaphthoquinonesulfonic acid phenyl ester)methane and 3 parts by weight of 4,4'-di-tert-butylphenyl iodide trifluorosulfonate were mixed with the above resin solution and stirred at room temperature for 2 hours. 5 parts by weight of 4,4'-methylenebis[2,6-bis(methoxymethyl)phenol] and 0.5 parts by weight of p-phenylenedimethoxysilane were added and stirred at room temperature for 2 hours to form a homogeneous solution. Finally, the solution was filtered with a 0.1μm filter membrane to obtain a homogeneous positive photosensitive polybenzoxazole resin composition solution.

[0079] The positive photosensitive polybenzoxazole resin compositions in Examples 2-9 and Comparative Examples 1-3 were prepared using the same method, and their compositions are shown in Table 1 (in parts by weight).

[0080] Among them, the compounds represented by each component code are as follows:

[0081] Sensitizer B:

[0082] B1: tris(1,2,5-diazonaphthoquinonesulfonatephenyl)methane;

[0083] B2: tris(1,2,5-diazonaphthoquinonesulfonic acid phenyl ester)-1-ethyl-4-isopropylbenzene;

[0084] B3: 2,3,4,4'-tetrakis(1,2,5-diazonaphthoquinonesulfonate)benzophenone.

[0085] Solvent C:

[0086] C1: γ-butyrolactone;

[0087] C2: N-methylpyrrolidone;

[0088] C3: Diethylene glycol dimethyl ether.

[0089] Photosensitive agent D:

[0090] D1: 4,4'-di-tert-butylphenyl iodide trifluorosulfonate;

[0091] D2: triphenylsulfonium perfluorobutanesulfonate;

[0092] D3: N-hydroxynaphthalimide trifluoromethanesulfonate.

[0093] Thermal crosslinker E:

[0094] E1: 4,4'-methylenebis[2,6-bis(methoxymethyl)phenol];

[0095] E2: 4-tert-butyl-2,6-bis(methoxymethyl)phenol.

[0096] Adhesion promoter F:

[0097] F1: p-isopropenylphenyltrimethoxysilane;

[0098] F2: Vinyltrimethoxysilane.

[0099] The specific mixing ratio is shown in Table 1 below:

[0100] Table 1

[0101]

[0102]

[0103] The evaluation of the positive photosensitive polybenzoxazole resin compositions in the above examples and comparative examples is shown in Table 2:

[0104] Table 2

[0105]

[0106]

[0107] Table 2 continued

[0108]

[0109] The aromatic silicon-containing polybenzoxazole precursor polymer of the present invention is obtained by polycondensing an aromatic silicon-containing diacid and its acyl halide with a hydroxyl-containing diamine by a known method. The introduction of the aromatic silicon-containing structure can improve the flexibility of the polymer molecular chain and reduce the rigidity. The silicon-oxygen structure has a good affinity for substrates such as silicon, glass, and ITO, thereby improving the bonding performance between the polybenzoxazole film and the substrate, enabling it to withstand the high temperature of the thermal cyclization process and complex operating environments. At the same time, the silicon-containing structure can further reduce hygroscopicity and internal stress, resulting in a low dielectric constant and high atomic oxygen resistance, thereby improving the reliability of microelectronic devices.

[0110] In terms of additive selection, the present invention selects one or a combination of two or more of a photosensitizing agent, a thermal crosslinking agent, and an adhesion promoter. The selection of a suitable photosensitizing agent can effectively reduce the energy required for exposure of the resin composition in conjunction with the photosensitizer, thereby improving sensitivity and imparting high photosensitivity. The selection of a suitable thermal crosslinking agent can enhance the alkaline water corrosion resistance of the unexposed portion of the resin film, helping to increase film retention and obtain high-resolution graphics. It can also improve the mechanical properties of the film after thermal cyclization. By omitting or selectively adding only a small amount of a high-temperature-resistant phenylsilicone-based adhesion promoter, self-condensation of high-content siloxanes can be prevented during storage, thereby improving storage stability.

[0111] Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A positive photosensitive polybenzoxazole resin composition, characterized in that: The invention is composed of the following components in parts by weight: 100 parts by weight of an aromatic silicon-containing polybenzoxazole precursor polymer, 1-50 parts by weight of a photosensitizer, 80-800 parts by weight of a solvent and additives; The additive is selected from one or a combination of two or more of a photosensitive auxiliary agent, a thermal crosslinking agent and an adhesion promoter, wherein the addition amount of the photosensitive auxiliary agent is 1-10 parts by weight, the addition amount of the thermal crosslinking agent is 5-20 parts by weight, and the addition amount of the adhesion promoter is 0.01-0.5 parts by weight; The general structure of the aromatic silicon-containing polybenzoxazole precursor polymer is represented by general formula (i), which is as follows: Wherein, R1 is a divalent organic group, serving as a residue of a dicarboxylic acid, and R2 is a tetravalent organic group, serving as a residue of a dihydroxydiamine; n is a positive integer, and the selected range is 20-60; The R1 of the dicarboxylic acid residue has an aromatic silicon-containing structure, and its general structural formula (ii) is shown as follows: in, 2. The positive photosensitive polybenzoxazole resin composition according to claim 1, characterized in that: The photosensitizer is a mixture of one or more of tris(1,2,5-diazonaphthoquinone sulfonic acid phenyl ester)methane, tris(1,2,5-diazonaphthoquinone sulfonic acid phenyl ester)-1-ethyl-4-isopropylbenzene, 2,3,4-tris(1,2,5-diazonaphthoquinone sulfonic acid ester)benzophenone, and 2,3,4,4'-tetrakis(1,2,5-diazonaphthoquinone sulfonic acid ester)benzophenone.

3. The positive photosensitive polybenzoxazole resin composition according to claim 1, characterized in that: The solvent is selected from one or a mixture of two or more of N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, propylene glycol methyl ether, cyclopentanone, cyclohexanone, methyl ethyl ketone, γ-butyrolactone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, butyl acetate, and propylene glycol methyl ether acetate.

4. The positive photosensitive polybenzoxazole resin composition according to claim 1, characterized in that: The photosensitive auxiliary agent is a photoacid generator, and the photoacid generator is an ionic acid generator, a non-ionic acid generator, or a mixture of the two; The ionic acid generator can be selected from one of 4,4'-di-tert-butylphenyl iodide trifluorosulfonate, perfluorobutylsulfonic acid triphenylsulfonium salt, 4,4'-ditolyl iodide hexafluorophosphate, 9,10-dimethoxy-2-anthracenesulfonic acid diphenyl iodide salt or a mixture of two or more thereof; The nonionic acid generator is a compound having the following structure:

5. The positive photosensitive polybenzoxazole resin composition according to claim 1, characterized in that: The photosensitive auxiliary agent is a thermal crosslinking agent, and the thermal crosslinking agent can be a compound with the following structure:

6. The positive photosensitive polybenzoxazole resin composition according to claim 1, characterized in that: The photosensitive auxiliary agent is an adhesion promoter, and the adhesion promoter is a silane coupling agent containing a phenyl silicon structure with excellent heat resistance. The silane coupling agent is selected from one of m-phenylenedimethoxysilane, m-phenyleneditriethoxysilane, p-phenyleneditriethoxysilane, p-phenyleneditrimethoxysilane, p-isopropenylphenyltriethoxysilane, and p-isopropenylphenyltrimethoxysilane, or a mixture of two or more thereof.

7. A method for preparing the positive photosensitive polybenzoxazole resin composition according to any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: adding the above-mentioned solvent into a glass or stainless steel container in a yellow light room, adding the synthesized aromatic silicon-containing polybenzoxazole precursor polymer, and stirring to completely dissolve it; adding the above-mentioned photosensitizer and the above-mentioned additives, stirring and dissolving them to obtain a homogeneous resin composition solution; and finally filtering the composition through a filter with a pore size of 0.1 μm to 5 μm to remove foreign matter to obtain a positive photosensitive polybenzoxazole resin composition.

8. Use of the positive photosensitive polybenzoxazole resin composition according to any one of claims 1 to 6, characterized in that: After coating, pre-baking, exposure, development and thermal curing steps, the application of the positive photosensitive polybenzoxazole resin composition is completed; the specific steps are as follows: (1) Coating: coating the positive photosensitive polybenzoxazole resin composition on a silicon substrate; (2) Pre-baking: heating and drying the silicon substrate coated with the positive photosensitive polybenzoxazole resin composition to remove the solvent and obtain a positive photosensitive resin film; (3) Exposure: Exposure is performed by irradiating ultraviolet light through a photomask having a desired pattern on the positive photosensitive resin film; (4) Development: After exposure, a developer is used to remove the exposed portion to obtain the desired pattern. (5) Thermal curing: The developed film is further heated to cure it on the substrate to obtain a positive photosensitive polybenzoxazole resin layer with the desired pattern.

9. The use of a positive photosensitive polybenzoxazole resin composition according to claim 8, characterized in that: The developer in step (4) is selected from one of an aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine.

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