A photosensitive polyimide composition with adjustable cone angle and use thereof

Abstract

The application belongs to the technical field of photosensitive material preparation, and particularly relates to a photosensitive polyimide composition with adjustable taper angle and application thereof. The photosensitive polyimide composition comprises a first diazonaphthoquinone sulfonate, a second diazonaphthoquinone sulfonate and a polyamide acid resin; the first diazonaphthoquinone sulfonate has a siloxane group. The first diazonaphthoquinone sulfonate has a siloxane group, which is easy to be combined with Si-OH bonds on a glass substrate, and a thin film formed by the photosensitive polyimide photoresist composition tends to be distributed on the lower layer. The two kinds of diazonaphthoquinone sulfonates are used in combination, and the difference in dissolution rate is utilized. In the alkali development process, the exposed part is dissolved slowly in the early stage of development and is dissolved quickly in the late stage of development, so that the bottom of the exposure part can reach the target critical dimension CD. The unexposed part is relatively fast in the dissolution of the upper sidewall in the early stage of development and is slow in the dissolution of the lower sidewall in the late stage of development, so that the taper angle (Taper angle) formed is small, and the technical effect of adjustable taper angle is achieved.

Description

Technical Field

[0001] This invention belongs to the field of photosensitive material preparation technology, specifically relating to a photosensitive polyimide composition with adjustable cone angle and its application. Background Technology

[0002] Photosensitive polyimide (PSPI) is a class of organic materials that possess both imine rings and photosensitive groups in their polymer chains, exhibiting excellent thermal stability, good mechanical properties, chemical properties, and photosensitivity. PSPI primarily serves two roles in the electronics field: photoresist and electronic packaging. Adding sensitizers and stabilizers to photosensitive polyimide yields "polyimide photoresist."

[0003] When PSPI photoresist is used in devices, the taper angle between the pattern and the substrate after exposure and development has a significant impact on subsequent material deposition. Therefore, it is necessary to develop a photosensitive polyimide composition with an adjustable taper angle to address various scenarios in practical applications. Summary of the Invention

[0004] Therefore, the technical problem to be solved by the present invention is to overcome the defects in the prior art, such as the inability to adjust the cone angle between the pattern and the substrate after exposure and development of PSPI photoresist applied to the device, which has a great impact on subsequent material deposition, thereby providing a photosensitive polyimide composition with adjustable cone angle and its application.

[0005] To this end, the present invention provides the following technical solution.

[0006] The first aspect of the present invention provides a photosensitive polyimide composition with an adjustable cone angle, comprising a first diazonaphthoquinone sulfonate, a second diazonaphthoquinone sulfonate, and a polyamic acid resin; wherein the first diazonaphthoquinone sulfonate has a siloxane group.

[0007] This invention uses two diazonaphthoquinone sulfonates in combination. After the photoresist is applied to the device, the cone angle between the pattern and the substrate after exposure and development ranges from 25 to 75°, and the cone angle has a large adjustable range.

[0008] In one alternative embodiment, the first diazonoquinone sulfonate has at least one of the following structural formulas:

[0009]

[0010] Wherein, D1, D2, and D3 are each independently selected from the following structural formula a or H, and at least one of D1, D2, and D3 is selected from the following structural formula a:

[0011]

[0012] In one alternative embodiment, the first diazonoquinone sulfonate has at least one of the following structural formulas:

[0013]

[0014] In one optional embodiment, the molar amount of structure a in the first diazonaphthoquinone sulfonate is 60%-95% of the total molar amount of D1, D2, and D3; for example, this ratio is 60%, 65%, 70%, 80%, 90%, 95%, etc.

[0015] In one alternative embodiment, the first diazonoquinone sulfonate has at least one of the following structural formulas:

[0016]

[0017]

[0018] It should be noted that the first diazonaphthoquinone sulfonate is preferably a mixture. The molar amount of structural formula a refers to the molar amount of structural formula a contained in the mixture. The total molar amount of D1, D2, and D3 refers to the sum of the molar amounts of all D1, D2, and D3 substitution sites in the mixture. The molar ratio is denoted as n1. The present invention achieves the control of n1 in the first diazonaphthoquinone sulfonate by adjusting parameters such as the raw material feeding ratio.

[0019] In one optional embodiment, the second diazonaphthoquinone sulfonate has the following structural formula:

[0020]

[0021] D4, D5, and D6 are each independently selected from the following structural formula a or H, and at least one of D4, D5, and D6 is selected from the following structural formula:

[0022]

[0023] In one alternative embodiment, the second diazonaphthoquinone sulfonate has at least one of the following structural formulas:

[0024]

[0025] In one alternative embodiment, the second diazonaphthoquinone sulfonate has at least one of the following structural formulas:

[0026]

[0027] In one optional embodiment, the molar amount of the second diazonaphthoquinone sulfonate structure a is 60%-95% of the total molar amount of D4, D5, and D6. Examples of such ratios include 60%, 65%, 70%, 80%, 90%, and 95%.

[0028] The second diazonaphthoquinone sulfonate is preferably a mixture. The molar amount of structural formula a refers to the molar amount of structural formula a contained in the mixture. The total molar amount of D4, D5, and D6 refers to the sum of the molar amounts of all D4, D5, and D6 substitution sites in the mixture. The molar ratio is denoted as n2. This invention achieves the control of the second diazonaphthoquinone sulfonate n2 by adjusting parameters such as the raw material feeding ratio.

[0029] In one optional embodiment, the mass ratio of the first diazonaphthoquinone sulfonate to the second diazonaphthoquinone sulfonate is (3-7):(7-3); exemplary values ​​include 3:7, 3:5, 3:3, 5:7, 5:3, 7:5, and 7:3. This invention adjusts the mass ratio of the first and second diazonaphthoquinone sulfonates. When photoresist is applied to a device, the cone angle between the pattern and the substrate after exposure and development can be adjusted. Different mass ratios of diazonaphthoquinone sulfonates can achieve cone angle adjustments within the range of 25-75°, providing a wide range of adjustable cone angles and broad applicability.

[0030] In one optional embodiment, the ratio of the total mass of the first diazonaphthoquinone sulfonate and the second diazonaphthoquinone sulfonate to the mass of the polyamic acid resin is (2-35):100; preferably, the ratio of the total mass of the first diazonaphthoquinone sulfonate and the second diazonaphthoquinone sulfonate to the mass of the polyamic acid resin is (5-25):100; exemplary, the ratio of the total mass of the first diazonaphthoquinone sulfonate and the second diazonaphthoquinone sulfonate to the mass of the polyamic acid resin is 2:100, 10:100, 15:100, 20:100, 25:100, 30:100, 35:100, etc.

[0031] In one optional embodiment, the mass content of the polyamic acid resin in the photosensitive polyimide composition with adjustable cone angle is 2-30%; for example, the mass content of the polyamic acid resin in the photosensitive polyimide composition with adjustable cone angle is 2%, 5%, 10%, 15%, 20%, 25%, 30%, etc.

[0032] In one optional embodiment, the polyamic acid resin has the following structural formula:

[0033]

[0034] Wherein, R1 is selected from acid dianhydrides with an alicyclic structure, R2 is selected from monocyclic or polycyclic aromatic diamine compounds, and R3 or R4 is selected from at least one of hydrogen, a hydrocarbon group having 1-10 carbon atoms, or a silane having 1-10 carbon atoms.

[0035] In one optional embodiment, the molar amount of hydrogen in the R3 group accounts for 20-60% of the total molar amount of all R3 groups; the molar amount of hydrogen in the R4 group accounts for 20-60% of the total molar amount of all R4 groups.

[0036] In this invention, the total molar amount of R3 groups in the amyl acid resin refers to the total molar amount of all R3 substitution sites in the polymer.

[0037] In one alternative implementation, n is 10-100; n is an integer, such as 10, 20, 30, 50, 65, 80, 88, 100, etc.

[0038] In one optional embodiment, the polyamic acid resin has a mass-average molecular weight of 5000-50000 g / mol.

[0039] In one optional embodiment, R1 is selected from at least one of 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride; preferably, R1 is 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride.

[0040] In one optional embodiment, R2 is selected from at least one of 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-diaminodiphenyl sulfide, and 4,4'-diaminobenzoylaniline; preferably, R2 is 2,2'-bis(trifluoromethyl)benzidine.

[0041] In one alternative embodiment, the photosensitive polyimide composition with adjustable cone angle further includes a thermal crosslinking agent, a surfactant, a solubility promoter, or a solvent;

[0042] In one optional embodiment, the thermal crosslinking agent is one or more of HMOM-TRHAP, TMOM-BPAP, NIKALAC MX-270, EPICLON-HP-4032, and EPICLON HP-7200, more preferably EPICLON-HP-4032;

[0043] In one optional embodiment, the surfactant is one or more of BYK-378, BYK-306, BYK-333, BYK-3760, KP-341, KP-358, KP-545, and KP-549; more preferably, the surfactant is BYK-333.

[0044] In one optional embodiment, the dissolution promoter is one or more of 4,4'-dihydroxybiphenyl, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, bisphenol A, and 4,4'-methylenebis(2,6-di-tert-butylphenol); more preferably, the dissolution promoter is 1,1,1-tris(4-hydroxyphenyl)ethane.

[0045] In one optional embodiment, the solvent is one or more of N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetone, methyl ethyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, and methyl lactate.

[0046] In one optional embodiment, the mass ratio of the polyamic acid resin, thermal crosslinking agent, surfactant, and solubility accelerator is 100:(5-40):(0.001-2):(5-30);

[0047] In one optional embodiment, the mass ratio of the polyamic acid resin, thermal crosslinking agent, surfactant, and solubility accelerator is 100:(10-25):(0.05-0.8):(5-25).

[0048] A second aspect of the present invention provides the application of the above-mentioned cone-angle adjustable photosensitive polyimide composition in wafer-level packaging redistribution layers, panel-level packaging redistribution layers, interlayer insulating layers of electronic components, or semiconductor surface protective films.

[0049] The technical solution of this invention has the following advantages:

[0050] 1. The present invention provides a photosensitive polyimide composition with adjustable taper angle, comprising a first diazonaphthoquinone sulfonate, a second diazonaphthoquinone sulfonate, and a polyamic acid resin; the first diazonaphthoquinone sulfonate has a siloxane group. The first diazonaphthoquinone sulfonate of the present invention has a siloxane group, which readily binds to Si-OH bonds on the glass substrate. In the photosensitive polyimide photoresist composition, the film formed tends to be distributed in the lower layer. The two diazonaphthoquinone sulfonates are used in combination, utilizing the difference in dissolution rates. During alkaline development, the exposed portion dissolves more slowly in the early stage of development and more quickly in the later stage, ensuring that the bottom of the exposed portion reaches the target critical dimension (CD). The unexposed portion dissolves relatively quickly on the upper sidewall in the early stage of development and less slowly on the lower sidewall in the later stage, resulting in a smaller taper angle and achieving the technical effect of adjustable taper angle. Furthermore, the first diazonaphthoquinone sulfonate has a siloxane group, which binds to Si-OH bonds on the glass substrate, increasing the adhesion between the film and the glass substrate, making the pattern less prone to detachment and improving device yield.

[0051] 2. The photosensitive polyimide composition with adjustable cone angle provided by the present invention can adjust the Taper angle by adjusting the amount of the two diazonaphthoquinone sulfonates, which is beneficial to adjust the cone angle to meet 25-75°, prevent the cone angle from being too large, and avoid situations such as incomplete bottom deposition. Attached Figure Description

[0052] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0053] Figure 1 This is a schematic diagram of the cone angle formed in the test example of the present invention. Detailed Implementation

[0054] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0055] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0056] Polyamic acid resins can be commercially available or prepared using methods known in the art. The preparation method of the polyamic acid resin used in the following examples includes the following steps:

[0057] Under a dry nitrogen stream, 2.24 g (10 mmol) of 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride, 3.2 g (10 mmol) of 2,2'-bis(trifluoromethyl)benzidine, 0.1 g of cyclohexanol (1 mmol), and 50 g of N-methylpyrrolidone were added to a 100 mL four-necked flask, and the mixture was heated and stirred at 60 °C. After 8 hours, the mixture was cooled to room temperature. The resulting mixture was poured into a large amount of deionized water to precipitate and wash, and then the white precipitate was filtered off. The precipitate filtration process was repeated three times. The resulting white polyamic acid polymer was dried in a vacuum oven for 72 hours to obtain polyamic acid resin powder.

[0058] The synthesized polymer was confirmed to meet the requirements using 1H NMR spectroscopy. The molecular weight of the polyamic acid was determined to be within the range of 18000±2000 g / mol using gel permeation chromatography. The proportion of hydrogen in the R3 group and the proportion of hydrogen in the R4 group of the polyamic acid were determined using acid-base neutralization reaction. The methods for determining the proportion of hydrogen in the R3 or R4 group included, but were not limited to, potentiometric titration of the carboxyl group content in the polyamic acid resin. Specifically, 0.5 g of the dried polyamic acid polymer was dissolved in 40 mL of N-methylpyrrolidone and 10 mL of methanol. The carboxyl groups in the polymer were titrated with 0.1 mmol / mL KOH methanol solution using a Shibata Scientific Instruments F702 titrator. The point of potential abrupt change was the titration endpoint, and the volume V of KOH used was recorded. Then, the percentage of carboxyl groups contained in 0.5g of polymer is obtained by calculating 0.1V / 50, which is the percentage of the total molar amount of all R3 or R4 groups with hydrogen as R3 or R4 groups.

[0059] The specific steps for obtaining the first diazonoquinone sulfonate include:

[0060] 1,1,1-Tris(4-hydroxyphenyl)ethane and liquid bromine reacted under light to produce 1,1,1-tris(4-hydroxyphenyl)bromoethane. The resulting 1,1,1-tris(4-hydroxyphenyl)bromoethane and 3-aminopropyltrimethoxysilane were then added to 100 mL of tetrahydrofuran (THF) solution and stirred at 50 °C for 3 h. The reaction mixture was then evaporated to dryness and subjected to column chromatography to obtain pure substance A. A and triethylamine were weighed and added to a 1,4-dioxane solvent. Substance B was then slowly added, and the reaction was allowed to proceed at room temperature for 5 h. The reaction mixture was then washed with a large amount of deionized water, and the solid was filtered off and dried under reduced pressure at room temperature for 48 h to obtain the target product, which includes the compounds shown in Formulas 7-9. The reaction process is as follows:

[0061]

[0062] The above products were characterized by NMR, and the results were as follows: 1 H NMR (CDCl3, 25°C): δ7.89-8.09 (d, 2.41H), δ7.75-7.86 (d, 2.38H), δ7.6-7.7 ( m, 2.39H), δ7.36 (d, 2.42H), δ7.1-7.13 (d, 6H), δ6.90-6.92 (d, 6H), δ6.21-6 The values ​​of δ25 (d, 3H), δ5.35 (s, 0.6H), δ3.55 (s, 9H), δ3.46 (s, 2H), δ2.55-2.57 (m, 2H), δ2.00-2.04 (m, 1H), δ1.46-1.52 (m, 2H), and δ0.58-0.63 (t, 2H) indicate that the above product was obtained.

[0063] In the preparation of diazonoquinone sulfonate, adjusting the molar ratio of A to B to 0.1:0.24 (i.e., 0.1 mol and 0.24 mol of A and B respectively) yields structure II-1 with an n1 of 80%; adjusting the molar ratio to 0.1:0.19 (i.e., 0.1 mol and 0.19 mol of A and B respectively) yields structure II-2 with an n1 of 60%; adjusting the molar ratio to 0.1:0.29 (i.e., 0.1 mol and 0.29 mol of A and B respectively) yields structure II-3 with an n1 of 95%. A molar ratio of A to B between 0.1:(0.19-0.29) is beneficial for achieving an n1 of 60-95%. Structures II-1, II-2, and II-3 all include compounds shown in formulas 7-9.

[0064] Following the above preparation method, replacing 3-aminopropyltrimethoxysilane with 3-aminopropyltriethoxysilane can synthesize didiazonaphthoquinone sulfonate III, including compounds shown in formula 10-12, where n1 is 80%. NMR characterization results: 1 H NMR (CDCl3, 25℃): δ7.89-8.09(d, 2.41H), δ7.75-7.86(d, 2.38H), δ7.6-7.7(m , 2.39H), δ7.36 (d, 2.42H), δ7.1-7.13 (d, 6H), δ6.90-6.92 (d, 6H), δ6.21-6.2 5(d, 3H), δ5.35(s, 0.6H), δ3.83(m, 6H), δ3.46(s, 2H), δ2.55-2.57(m, 2H), δ2 .00-2.04 (m, 1H), δ1.46-1.52 (m, 2H), δ1.21-1.24 (t, 9H), δ0.58-0.63 (t, 2H).

[0065] Following the above preparation method, replacing 3-aminopropyltrimethoxysilane with γ-aminoethylaminopropyltrimethoxysilane can synthesize didiazonaphthoquinone sulfonate IV, including compounds shown in formulas 13-15, where n1 is 80%. NMR characterization results: 1 H NMR (CDCl3, 25°C): δ7.89-8.09 (d, 2.41H), δ7.75-7.86 (d, 2.38H), δ7.6- 7.7 (m, 2.39H), δ7.36 (d, 2.42H), δ7.1-7.13 (d, 6H), δ6.90-6.92 (d, 6H), δ6.21-6.25 (d, 3H), δ5.35 (s, 0.6H), δ3.55 (s, 9H), δ3.46 (s, 2H), δ2.5-2 .60 (m, 6H), δ2.00-2.04 (m, 1H), δ1.46-1.52 (m, 2H), δ0.58-0.63 (t, 2H).

[0066] Those skilled in the art can control the feed ratio to adjust the value of n1 in first diazonaphthoquinone sulfonate III and first diazonaphthoquinone sulfonate IV.

[0067] The specific steps for obtaining didiazonaphthoquinone sulfonate include:

[0068] 1,1,1-tris(4-hydroxyphenyl)ethane and triethylamine were weighed and added to a 1,4-dioxane solvent. Substance B was then slowly added, and the reaction was allowed to proceed at room temperature for 5 hours after the addition was complete. The reaction solution was then added to a large volume of deionized water and washed with stirring. Finally, the solid was filtered off and dried under reduced pressure at room temperature for 48 hours to obtain the target product. The reaction process is as follows:

[0069]

[0070] The diazonoquinone sulfonate obtained according to the above preparation method is a mixture comprising the three compounds described in formulas 18-20, with n2 being 80%.

[0071] The calculation method for the ratios n1 and n2 of the structural formula a of the first and second diazononaphthoquinone sulfonates to the total molar amount of D is illustrated using the first diazononaphthoquinone sulfonate II as an example:

[0072] The synthesized first diazonaphthoquinone sulfonate II was dissolved in acetonitrile and analyzed using an Agilent 1200 high-performance liquid chromatograph. Three peaks appeared in the chromatogram, corresponding to compounds of structural formulas 7, 8, and 9, respectively. The peak areas were then integrated to obtain Y1, Y2, and Y3, corresponding to compounds of structural formulas 7-9, respectively. The substitution ratio was calculated as n1 = (Y1 + 2Y2 + 3Y3) / 3(Y1 + 2Y2 + 3Y3) × 100%. Similarly, the ratios n1 or n2 of other diazonaphthoquinone sulfonates of structural formula a to the total molar amount of D were obtained.

[0073] Examples 1-9 and Comparative Examples 1-4

[0074] The examples and comparative examples provide a photosensitive polyimide composition with an adjustable cone angle. The mixture was prepared according to the amounts in Table 1, shaken in a shaker for 4 hours, filtered through a 0.22 μm filter membrane, and then shaken for another 1 hour after filtration.

[0075] Table 1. Content of each component in the photosensitive polyimide compositions of the examples and comparative examples.

[0076]

[0077] Note: The polyamic acid resin is calculated in parts by weight. The amounts of each raw material are shown in Table 1. The surfactant used in each example and comparative example is BYK-333, which is 0.05 parts. The mass concentration of polyamic acid resin in the compositions of each example and comparative example is 10%. The solvent includes propylene glycol monomethyl ether: ethyl lactate: γ-butyrolactone in a mass ratio of 7:2:1. The amount of solvent was obtained according to the concentration of polyamic acid resin in the composition and the amount of other raw materials. "-" indicates that the corresponding substance is not present.

[0078] Test case

[0079] This test case provides the performance test results for each embodiment and comparative example, as follows:

[0080] The method for testing the Taper angle is as follows: A spin coater is used to coat the photosensitive polyimide photoresist composition at 500 rpm for 5 seconds, followed by a spin coater speed of 1000 rpm for 30 seconds. The mixture is then heated to 120°C for 120 seconds to obtain a glass slide coated with the photoresist. Exposure is performed using an ABM / 6 / 350 / NUV / DCCD / BSV / M lithography machine at an energy of 50 mJ / cm². 2 The process involved development, curing, and microscopic observation of the 3μm pores to determine if they met the set CD value. Subsequently, focused ion dual-beam microscopy (FIB-SEM) was used to test patterns that met the set CD value; a schematic diagram of the resulting cone angle is shown below. Figure 1 .

[0081] Adhesion testing method: The cross-cut adhesion test is used, and according to Japanese Industrial Standards (JIS), it is divided into 1-5 levels, with higher levels indicating stricter requirements. Level 1 indicates that there is large-scale peeling at the edges and intersections of the cross-cuts, and the total peeling area S is between 35% < S ≤ 65%; Level 2 indicates that there is large-scale peeling at the edges and intersections of the cross-cuts, and the total peeling area is between 15% < S ≤ 35%; Level 3 indicates that there is small-scale peeling at the edges and intersections of the cross-cuts, and the total peeling area is between 5% < S ≤ 15%; Level 4 indicates that there is small-scale peeling at the intersections of the cross-cuts, and the total peeling area is less than S ≤ 5%; Level 5 indicates that there is absolutely no peeling.

[0082] Table 2 Performance test results of each embodiment and comparative example

[0083]

[0084] As seen in the above embodiments, when forming the photoresist, the first diazonaphthoquinone sulfonate and the second diazonaphthoquinone sulfonate of the present invention are used in combination. Adjusting the amount of the two sulfonates can achieve the technical effect of adjustable cone angle, which is adjustable within the range of 25-75°. Examples 1-9 show that the higher the mass ratio of the first diazonaphthoquinone sulfonate to the second diazonaphthoquinone sulfonate, the smaller the resulting cone angle. This indicates that adjusting the amount of these two substances can achieve cone angle adjustment within the range of 25-75°. Those skilled in the art can adjust the amount of the two sulfonates to obtain a composition that meets the expected cone angle requirements.

[0085] Comparative Examples 1-4 show that when the amount of didiazonaphthoquinone sulfonate is high or low, the cone angle is around 75° when forming the photoresist. Adjusting its amount cannot achieve the technical effect of adjustable cone angle. Looking at Comparative Example 4, even after adding KH-550, the cone angle does not change significantly when forming the photoresist, remaining around 75°. This indicates that adjusting the amount of didiazonaphthoquinone sulfonate alone cannot achieve the technical effect of adjustable cone angle.

[0086] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A photosensitive polyimide composition with an adjustable cone angle, characterized in that, It includes a first diazonaphthoquinone sulfonate, a second diazonaphthoquinone sulfonate, and a polyamic acid resin; the first diazonaphthoquinone sulfonate has a siloxane group; The first diazonoquinone sulfonate has at least one of the following structural formulas: ， Wherein, D1, D2, and D3 are each independently selected from the following structural formula a or H, and at least one of D1, D2, and D3 is selected from the following structural formula a: Formula a; The second diazonoquinone sulfonate has the following structural formula: D4, D5, and D6 are each independently selected from the following structural formula a or H, and at least one of D4, D5, and D6 is selected from the following structural formula: Formula a.

2. The photosensitive polyimide composition with adjustable cone angle according to claim 1, characterized in that, The first diazonoquinone sulfonate has at least one of the following structural formulas: 。 3. The photosensitive polyimide composition with adjustable cone angle according to claim 1 or 2, characterized in that, The molar amount of structural formula a in the first diazonaphthoquinone sulfonate ester accounts for 60%-95% of the total molar amount of D1, D2, and D3; and / or, The first diazonoquinone sulfonate has at least one of the following structural formulas: 。 4. The photosensitive polyimide composition with adjustable cone angle according to claim 1, characterized in that, The second diazonoquinone sulfonate has at least one of the following structural formulas: ； And / or, the molar amount of the second diazonaphthoquinone sulfonate structure a accounts for 60%-95% of the total molar amount of D4, D5, and D6.

5. The photosensitive polyimide composition with adjustable cone angle according to claim 4, characterized in that, The second diazonoquinone sulfonate has at least one of the following structural formulas: 。 6. The photosensitive polyimide composition with adjustable cone angle according to claim 1 or 2, characterized in that, The mass ratio of the first diazonaphthoquinone sulfonate to the second diazonaphthoquinone sulfonate is (3-7):(7-3); And / or, the ratio of the total mass of the first diazonaphthoquinone sulfonate and the second diazonaphthoquinone sulfonate to the mass of the polyamic acid resin is (2-35):100; And / or, the mass content of the polyamic acid resin in the photosensitive polyimide composition with adjustable cone angle is 2-30%.

7. The photosensitive polyimide composition with adjustable cone angle according to claim 6, characterized in that, The ratio of the total mass of the first diazonaphthoquinone sulfonate and the second diazonaphthoquinone sulfonate to the mass of the polyamic acid resin is (5-25):

100.

8. The photosensitive polyimide composition with adjustable cone angle according to claim 1 or 2, characterized in that, It also includes thermal crosslinking agents, surfactants, dissolution promoters, or solvents.

9. The photosensitive polyimide composition with adjustable cone angle according to claim 8, characterized in that, The thermal crosslinking agent is one or more of HMOM-TRHAP, TMOM-BPAP, NIKALAC MX-270, EPICLON-HP-4032, and EPICLON HP-7200; And / or, the surfactant is one or more of BYK-378, BYK-306, BYK-333, BYK-3760, KP-341, KP-358, KP-545, and KP-549; And / or, the solubility promoter is one or more of 4,4'-dihydroxybiphenyl, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, bisphenol A, and 4,4'-methylenebis(2,6-di-tert-butylphenol); And / or, the solvent is one or more of N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetone, methyl ethyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, and methyl lactate. And / or, the mass ratio of the polyamic acid resin, thermal crosslinking agent, surfactant, and solubility accelerator is 100:(5-40):(0.001-2):(5-30); And / or, the mass ratio of the polyamic acid resin, thermal crosslinking agent, surfactant, and solubility accelerator is 100:(10-25):(0.05-0.8):(5-25).

10. The photosensitive polyimide composition with adjustable cone angle according to claim 9, characterized in that, The thermal crosslinking agent is EPICLON-HP-4032; And / or, the surfactant is BYK-333; And / or, the solubility promoter is 1,1,1-tris(4-hydroxyphenyl)ethane.

11. The use of the photosensitive polyimide composition with adjustable cone angle according to any one of claims 1-10 in a wafer-level packaging redistribution layer, a panel-level packaging redistribution layer, an interlayer insulating layer for electronic components, or a semiconductor surface protective film.

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