High-adhesion negative photosensitive resin composition, method of manufacturing and use thereof

Abstract

The application provides a negative photosensitive resin composition, a preparation method and application thereof. The negative photosensitive resin composition comprises: 5-30 parts by mass of a polyimide precursor; 1-5 parts by mass of a primary amine hydrochloride; 1-5 parts by mass of a photoinitiator; and 1-5 parts by mass of a crosslinking agent. The viscosity of the polyimide precursor is 300-2000 cps. The weight average molecular weight of the polyimide precursor is 40000-45000. The application further discloses a preparation method of the negative photosensitive resin composition and application thereof. The negative photosensitive resin prepared by the application has excellent adhesion, high-temperature resistance and film-forming stability, and has good application prospect and large-scale industrialization potential in the field of semiconductors and integrated circuits.

Description

Technical Field

[0001] This invention relates to polymer materials technology, and more particularly to a negative photosensitive resin composition with high adhesion, its preparation method, and its application. Background Technology

[0002] Photosensitive polyimide (PSPI) is a high-performance polymer material with excellent electrical, mechanical, and thermal stability properties. It also has a low coefficient of thermal expansion, good resistance to water and organic solvents, and can absorb α-particles. It has been widely used in integrated circuit manufacturing.

[0003] Photosensitive polyimides are classified into positive and negative types, with negative photosensitive polyimides becoming a research hotspot in recent years. Photosensitive polyimides are further divided into polyamide ester type and polyamide salt type. Due to the poor adhesion between existing polyimide compositions and substrates, problems such as residual adhesive and adhesive drift easily occur during development, thus affecting the yield in integrated circuit manufacturing.

[0004] Therefore, developing a negatively photosensitive polyimide that combines high adhesion and high temperature resistance has become a research direction that needs to be further promoted. Summary of the Invention

[0005] The purpose of this invention is to address the problem of low adhesion of traditional polyimide, which affects the yield of integrated circuits, by proposing a negative photosensitive resin composition with high adhesion. This negative photosensitive resin composition has excellent adhesion, high temperature resistance and film-forming stability, and has good application prospects and potential for large-scale industrial promotion in the semiconductor and integrated circuit fields.

[0006] It should be noted that, in this invention, unless otherwise specified, the specific meaning of "comprising" in relation to composition and description includes both open-ended meanings such as "comprising," "including," etc., and closed-ended meanings such as "composed of," "consisting of," etc., and similar meanings.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is: a highly adhesive negative photosensitive resin composition, comprising:

[0008] 15-30 parts by weight of polyimide precursor;

[0009] 1-5 parts by weight of primary amine hydrochloride;

[0010] 1-5 parts by weight of photoinitiator;

[0011] 1-5 parts by weight of crosslinking agent;

[0012] The primary amine hydrochloride has the following structural formula:

[0013] , , or ;

[0014] Where p, q, r, and s are any integers from 1 to 5.

[0015] The present invention relates to a polyimide precursor (hereinafter sometimes also referred to as "polyimide resin", "polyimide precursor", or "polyamic acid ester", all of which have the same meaning).

[0016] Further, the primary amine hydrochloride is one or more of heptanol hydrochloride, L-lysine hydrochloride, 5-hydroxytryptamine hydrochloride, and 3-hydroxy-4-methoxybenzylamine hydrochloride.

[0017] Furthermore, the primary amine hydrochloride is present in amounts of 1-4 parts.

[0018] The primary amine hydrochloride of this invention can react and enter the system, playing multiple roles and effectively improving development stability. Specifically, it can interrupt the excessive growth of molecular chains in the reaction system, controlling the molecular weight and molecular weight distribution within a certain range. On the other hand, due to the presence of hydroxyl groups in the primary amine hydrochloride, hydrogen bonds will form between it and the substrate after spin-coating of the negative PSPI, which can increase the adhesion between the negative PSPI and different substrates and solve the problem of small-sized lines falling off during development. In summary, the use of primary amine hydrochloride can effectively improve development stability.

[0019] Further, the photoinitiator is one or more of dibenzoyl-p-quinone dioxime, acetylbenzene O-benzoyl oxime, and ethyl O-(2,4,6-trimethylbenzenesulfonyl)acetylhydroxyoxime.

[0020] Furthermore, the photoinitiator is 2-5 parts.

[0021] Furthermore, the crosslinking agent is a compound containing acrylate groups.

[0022] Further, the crosslinking agent is preferably one or more selected from tetraethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane diacrylate, and 2-hydroxyethyl acrylate.

[0023] Furthermore, the crosslinking agent is 1-4 parts.

[0024] Furthermore, the viscosity of the polyimide precursor is 300-2000 cps. The viscosity of the polyimide precursor reflects the molecular weight to some extent. If the viscosity exceeds this range, it indicates that the molecular weight is too high, which affects the resolution of the negative photosensitive resin composition after exposure and development.

[0025] Furthermore, the weight-average molecular weight of the polyimide precursor is 40,000-45,000.

[0026] Furthermore, the polyimide precursor has the following structural formula:

[0027]

[0028] Wherein, R1 is a tetravalent organic group, R2 is a divalent organic group, R3 and R4 are both monovalent organic groups with carbon-carbon unsaturated double bonds, and n is an integer from 2 to 140.

[0029] Furthermore, in the polyimide precursor, R1 is derived from a tetravalent organic group obtained by removing two anhydride groups from a dianhydride; R2 is derived from a divalent organic group obtained by removing two amino groups from a diamine.

[0030] Furthermore, the dianhydride is a phenyl dianhydride compound.

[0031] Further, the dianhydride is preferably one or more of 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, and pyromellitic dianhydride.

[0032] Furthermore, the diamine is a phenylenediamine compound.

[0033] Further, the diamine is preferably one or more of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether, 1,3-bis(4-aminophenoxy)benzene, 3,3'-dihydroxybenzidine, and 3,3',5,5'-tetramethylbenzidine.

[0034] Furthermore, R3 and R4 are both residues of an esterifying agent, which is an olefinic unsaturated compound containing multiple carbon-carbon double bonds, which can be either conjugated or non-conjugated.

[0035] Furthermore, the esterifying agent is preferably a polyfunctional propylene monomer.

[0036] Further, the esterifying agent is more preferably one or more of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl 2-methacrylate, hydroxypropyl methacrylate, and 2-hydroxy-3-phenoxypropyl methacrylate.

[0037] Another object of the present invention discloses a method for preparing a highly adhesive negative photosensitive resin composition, comprising the following steps:

[0038] Photoinitiator, crosslinking agent, and primary amine hydrochloride were added to the purified polyimide precursor and stirred to obtain a highly adhesive photosensitive resin composition.

[0039] Furthermore, the stirring time is 8-16 hours.

[0040] Furthermore, in this invention, the preparation of the polyimide precursor adopts a preparation process well known to those skilled in the art, using diamine and dianhydride well known to those skilled in the art as raw materials for preparing the polyimide precursor. In the presence of a catalyst, the dianhydride and esterifying agent are dissolved in an organic solvent, and then a chlorinating agent and diamine are added to obtain the polyimide precursor.

[0041] Furthermore, the dianhydride is a phenyl dianhydride compound.

[0042] Further, the dianhydride is preferably one or more of 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, and pyromellitic dianhydride.

[0043] Furthermore, the dianhydride is 10-20 parts.

[0044] Furthermore, the esterifying agent is an olefinic unsaturated compound containing multiple carbon-carbon double bonds, which can be either conjugated or non-conjugated.

[0045] Furthermore, the esterifying agent is preferably a polyfunctional propylene monomer.

[0046] Further, the esterifying agent is more preferably one or more of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl 2-methacrylate, hydroxypropyl methacrylate, and 2-hydroxy-3-phenoxypropyl methacrylate.

[0047] Furthermore, the catalyst is an organic base.

[0048] Furthermore, the catalyst is preferably one of pyridine, triethylamine, and triethanolamine.

[0049] Furthermore, the chlorinating agent is one or more of thionyl chloride, thiosulfate, oxalyl chloride, and phosphorus trichloride.

[0050] Furthermore, the diamine is a phenylenediamine compound.

[0051] Further, the diamine is preferably one or more of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether, 1,3-bis(4-aminophenoxy)benzene, 3,3'-dihydroxybenzidine, and 3,3',5,5'-tetramethylbenzidine.

[0052] Further, by mass parts, the dianhydride is 10-20 parts; the diamine is 5-10 parts; the catalyst is 2-5 parts; the esterifying agent is 5-10 parts; and the chlorinating agent is 2-5 parts.

[0053] Furthermore, the organic solvent is one or more of alcohols, ketones, nitriles, ethers, esters, sulfur-containing compounds, or nitrogen-containing compounds.

[0054] Further, the organic solvent is preferably one or more selected from methanol, ethanol, propanol, n-propanol, ethyl acetate, acetone, formamide, dioxane, dichloromethane, chloroform, bromoethane, cyclohexane, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, tetrahydrofuran, cyclopentanone, and dimethyl sulfoxide.

[0055] Furthermore, in this invention, the amount of the organic solvent is not limited, as long as it is sufficient to dissolve the corresponding dianhydride, diamine, esterifying agent, and other components. The organic solvent is 30-50 parts by mass.

[0056] Furthermore, in this invention, the method for purifying the polyimide precursor is as follows:

[0057] The prepared polyimide precursor is dissolved in a solvent to obtain a product slurry; then the product slurry is dropped into a poor solvent, and the polyimide precursor will precipitate in the form of powder. The powder is then filtered, collected, and dried. The above operation is repeated at least twice to complete the purification.

[0058] Furthermore, the solvent may be the same as or different from an organic solvent, and the solvent may be one or more of alcohols, ketones, nitriles, ethers, esters, sulfur-containing compounds, or nitrogen-containing compounds.

[0059] Further, the solvent is preferably one or more selected from methanol, ethanol, propanol, n-propanol, ethyl acetate, acetone, formamide, dioxane, dichloromethane, chloroform, bromoethane, cyclohexane, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, tetrahydrofuran, cyclopentanone, and dimethyl sulfoxide.

[0060] In this invention, the amount of solvent is not limited, but is sufficient to dissolve the polyimide precursor. A suitable ratio of the mass of the polyimide precursor to the solvent is 1:5-20.

[0061] Furthermore, the amount of the undesirable solvent used is not less than 10 times the weight of the product slurry.

[0062] Furthermore, in this invention, any type of unsuitable solvent can be used to separate the polyimide precursor from the product slurry. Suitable unsuitable solvents include one or more of deionized water, methanol, ethanol, dichloromethane, petroleum ether, acetone, isopropanol, diethyl ether, n-hexane, ethyl acetate, and chloroform.

[0063] Furthermore, the undesirable solvent is preferably one or more of deionized water, methanol, ethanol, dichloromethane, and petroleum ether.

[0064] Another object of the present invention is to disclose the application of a highly adhesive negative photosensitive resin composition in the semiconductor field.

[0065] Furthermore, the highly adhesive negative photosensitive resin composition is particularly suitable for semiconductor encapsulation.

[0066] Furthermore, the method for preparing micron-level patterns using the highly adhesive negative photosensitive resin composition includes the following steps: coating the highly adhesive negative photosensitive resin composition onto a substrate, and sequentially subjecting it to baking, exposure, secondary baking, and development treatment to obtain a developed pattern.

[0067] The highly adhesive negative photosensitive resin composition, when exposed during use, will induce free radical polymerization in the composition, cross-linking the exposed areas, reducing solubility, and preventing it from being washed away by the developer; the thermal imidization process then heats and solidifies the remaining pattern, converting it into polyimide, which is retained as a stress buffer layer, insulating layer, etc.

[0068] This invention discloses a highly adhesive negative photosensitive resin composition, its preparation method, and its application, which have the following advantages compared with the prior art:

[0069] This invention creatively introduces primary amine hydrochloride, which significantly improves the overall performance of negative polyimide (PSPI). Specifically, the introduction of primary amine hydrochloride effectively interrupts the excessive growth of molecular chain length in the reaction system, controlling the molecular weight and molecular weight distribution within a reasonable range. On the other hand, after spin coating, the resulting negative PSPI forms hydrogen bonds with the substrate, which can increase the adhesion of negative PSPI to different substrates.

[0070] 2. The high-adhesion negative photosensitive resin composition of the present invention can effectively resist the energy generated by thermal excitation in its molecular structure under high temperature environment, and is not easy to break, thereby maintaining the integrity of the molecular chain and endowing the negative photosensitive resin composition with high temperature resistance.

[0071] Therefore, the high-adhesion negative photosensitive resin composition of the present invention, with its excellent adhesion, high temperature resistance and film-forming stability, has very good application prospects and potential for large-scale industrial promotion in the semiconductor and integrated circuit fields. Attached Figure Description

[0072] Figure 1 The cross-sectional morphology of a 20 μm wide line under SEM after exposure and development using the highly adhesive negative photosensitive resin composition of Example 1, magnified 2000 times;

[0073] Figure 2 The cross-sectional morphology of a 20μm wide line under SEM after exposure and development of the polymer material in Comparative Example 1 is shown at a magnification of 2000x.

[0074] Figure 3 Microscopic image of the high-adhesion negative photosensitive resin composition of Example 1 after exposure and development, magnified 50 times;

[0075] Figure 4 The image is a microscope image after exposure and development of the polymer material used in Comparative Example 1, magnified 50 times.

[0076] Figure 5 The NMR spectrum is shown for the highly adhesive negative photosensitive resin composition of Example 1. Detailed Implementation

[0077] The present invention will be further described below with reference to embodiments. The description of the technical features described below is based on representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:

[0078] Unless otherwise stated, all units used in this specification are international standard units, and all numerical values ​​and ranges appearing in this invention should be understood to include systematic errors that are unavoidable in industrial production.

[0079] In this specification, the range of values ​​referred to as "value A to value B" refers to the range including the endpoint values ​​A and B.

[0080] In this specification, the numerical range indicated by "above" or "below" refers to the numerical range that includes the stated number.

[0081] In this specification, the word "may" has two meanings: to perform a certain process and not to perform a certain process.

[0082] In this specification, the terms "optional" or "optional" are used to indicate the use or omission of certain substances, components, procedures, application conditions, etc.

[0083] In this instruction manual, when "room temperature" or "room temperature" is used, the temperature can be 15-25℃.

[0084] Unless otherwise specified, all reagents or instruments used in this instruction manual are commercially available products.

[0085] Examples 1-6

[0086] Examples 1-6 disclose various highly adhesive negative photosensitive resin compositions, the preparation methods of which include the following steps:

[0087] S1: Dissolve dianhydride and esterifying agent in an organic solvent and react under catalytic conditions to obtain diacid diester; then add chlorinating agent to react and obtain acyl chloride; finally add diamine to react and obtain polyimide precursor.

[0088] The prepared polyimide precursor was dissolved in a solvent (in this embodiment, the solvent and organic solvent are the same, and the amount of solvent is 10 times the mass of the polyimide precursor) to obtain a product slurry; then the product slurry was dropped into deionized water (in this embodiment, the amount of deionized water is 10 times the mass of the product slurry), and the polyimide precursor precipitated in the form of powder. The powder was then filtered, collected, and dried. The above operation was repeated twice to complete the purification.

[0089] S2: Add the photoinitiator, crosslinking agent, and primary amine hydrochloride to the purified polyimide precursor and stir for 12 h to obtain a negative photosensitive resin composition with high adhesion.

[0090] The raw materials and formulations used in the preparation method of the highly adhesive negative photosensitive resin composition are shown in Table 1.

[0091] Table 1. Raw materials and proportions of the high-adhesion negative photosensitive resin compositions in Examples 1-6

[0092]

[0093] Comparative Examples 1-3

[0094] Comparative Examples 1-3 disclose a variety of polymer materials, the preparation methods of which are the same as those in Example 1. The raw materials and formulations used in the preparation process are shown in Table 2.

[0095] Table 2 Raw materials and proportions of polymer materials in Comparative Examples 1-3

[0096]

[0097] The high-adhesion negative photosensitive resin compositions of Examples 1-6 and the polymer materials of Comparative Examples 1-3 were tested respectively. The test methods and test results are as follows:

[0098] Table 3 Test Results

[0099]

[0100] As can be seen from Table 3, the molecular weight of the high-adhesion negative photosensitive resin compositions in Examples 1-6 is controlled between 40,000 and 45,000, and the adhesion to the substrate is 3B or higher, exhibiting high adhesion. The 1% thermal weight loss temperature is above 400°C, and no problems such as residual glue or glue drift occur during the development process.

[0101] Comparative Example 1 showed a complete deterioration in performance due to the absence of primary amine hydrochloride; Comparative Examples 2 and 3, which used non-specific primary amine hydrochlorides (hexylamine hydrochloride and 2-chloroethylamine hydrochloride), failed to achieve the expected results.

[0102] from Figure 1 It can be seen that the pattern obtained by exposure and development using the high-adhesion negative photosensitive resin composition of Example 1 adheres firmly to the substrate and has good adhesion. Figure 2 It can be seen that the pattern obtained by exposure and development of the polymer material in Comparative Example 1 is partially separated from the substrate, indicating poor adhesion; through Figure 1 and Figure 2 Comparative studies have shown that modifying the resin with primary amine hydrochloride can significantly improve the adhesion between the composition and the substrate.

[0103] from Figure 3 It can be seen that after exposure and development using the high-adhesion negative photosensitive resin composition of Example 1, the overall pattern is good, with no residual resin or drift resin. Figure 4 It can be seen that after exposure and development of the polymer material in Comparative Example 1, the overall pattern exhibits large-area glue drift, indicating poor patterning performance. Figure 3 and Figure 4 The comparison demonstrates that the highly adhesive photosensitive resin composition of the present invention has excellent patterning properties.

[0104] Example 1: The chemical structure of the highly adhesive negative photosensitive resin composition was characterized by NMR spectroscopy (using deuterated DMSO as solvent). Figure 5 It can be seen that the characteristic peaks of the methyl group on heptanol hydrochloride appear at 1.09 ppm and 1.22 ppm in the 1H NMR spectrum, and the characteristic peak of the hydroxyl group on heptanol hydrochloride appears at 3.48 ppm. At the same time, there are no characteristic peaks of amino groups in the 1.55-1.65 ppm region, which indicates that heptanol hydrochloride has been introduced into the system.

[0105] The test method for performance 1 is as follows:

[0106] The product (negative photosensitive resin composition or polymer material) is spin-coated onto a silicon wafer and cured at high temperature. A grid is scraped out using a grid cutter. The wafer is then treated at 120°C and a certain humidity for a certain period of time, removed and dried. The grid is then adhered using tape. The adhesion is judged based on the number of grids remaining.

[0107] If there is no peeling, the rating is 5B; if the damage is less than 5%, it is 4B; if the peeling area is greater than 5% but less than 15%, it is 3B; if the peeling area is greater than 15% but less than 35%, it is 2B; if the peeling area is greater than 35% but less than 65%, it is 1B; if the peeling area is greater than 65%, it is 0B.

[0108] The test method for performance 2 is as follows:

[0109] (1) The product is coated onto the substrate by spin coating at a speed of 4000 r / min to form an adhesive layer.

[0110] (2) The adhesive layer obtained in step (1) is baked at 120°C for 120s to obtain a uniform film with a thickness of 20μm.

[0111] (3) Expose the thin film prepared in step (2) with an exposure wavelength of 365 nm and an exposure dose of 500 mJ / cm. 2 .

[0112] (4) Bake the film exposed in step (3) at 120°C for 120 seconds.

[0113] (5) The film that has been baked in step (4) is then developed in a developing device. Using a conventional microscope at 50x magnification, the presence or absence of residual adhesive and adhesive drift can be observed more directly. See the test results for details. Figure 3 and Figure 4 .

[0114] The testing method for Performance 3 is as follows:

[0115] Cut the product film into fragments, place the fragments into a crucible using antistatic tweezers, and set the program to test the 1% thermogravimetric temperature loss.

[0116] The testing method for performance level 4 is as follows:

[0117] The graphic obtained from the performance 2 test method is cut using a blade or laser, exposing the cross-section of the graphic. The cut graphic is then subjected to scanning electron microscopy (SEM) testing at 2000x magnification, followed by imaging. The test results are shown in [reference needed]. Figure 1 and Figure 2 .

[0118] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A negative photosensitive resin composition, characterized by comprising: Comprise: polyimide precursor 15-30 parts by mass; primary amine hydrochloride 1-5 parts by mass; photoinitiator 1-5 parts by mass; crosslinking agent 1-5 parts by mass; The primary amine hydrochloride has the following structural formula: , , or ; Wherein, p, q, r, s are any integer from 1 to 5 respectively; The polyimide precursor has the following structural formula: ； Wherein, R1 is a four-valent organic group, R2 is a two-valent organic group, R3 and R4 are both monovalent organic groups with carbon-carbon unsaturated double bonds, and n is an integer from 2 to 140.

2. The negative photosensitive resin composition according to claim 1, wherein The primary amine hydrochloride is one or more of heptylamine hydrochloride, L-lysine hydrochloride, 5-hydroxytryptamine hydrochloride, and 3-hydroxy-4-methoxybenzylamine hydrochloride; And / or, the photoinitiator is one or more of dibenzoyl-p-benzoquinone dioxime, acetylbenzene O-benzoyl oxime, and O-(2,4,6-trimethylbenzenesulfonyl) acetyl hydroxamic acid ethyl ester; And / or, the crosslinking agent is a compound containing an acrylate group.

3. The negative photosensitive resin composition according to claim 1, wherein The viscosity of the polyimide precursor is 300-2000 cps.

4. The negative photosensitive resin composition according to claim 1, wherein The weight average molecular weight of the polyimide precursor is 40000-45000.

5. The negative photosensitive resin composition according to claim 4, wherein The preparation method of the polyimide precursor comprises the following steps: dissolving dianhydride and esterifying agent in organic solvent in the presence of catalyst, then adding chlorinating agent and diamine to obtain polyimide precursor.

6. A method for producing the negative photosensitive resin composition according to any one of claims 1 to 5, characterized by, Comprise the following steps: The photoinitiator, crosslinking agent and primary amine hydrochloride are added to the purified polyimide precursor, and stirring is carried out to obtain a negative photosensitive resin composition.

7. The method for preparing the negative photosensitive resin composition according to claim 6, characterized in that, The pH of the reaction system is 5-7.

8. Use of the negative photosensitive resin composition of any one of claims 1-5 in the field of semiconductors.

9. Use according to claim 8, characterized in that, A method for preparing a micron-level pattern using the negative photosensitive resin composition, comprising the following steps: The negative photosensitive resin composition is coated on a substrate, and is subjected to baking, exposure, secondary baking and development treatment in sequence to obtain a micron-level developed pattern.

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