Negative photosensitive resin composition, method for producing cured relief pattern, and semiconductor device

Abstract

The invention relates to a negative photosensitive resin composition, a method for manufacturing a cured relief pattern, and a semiconductor device. The negative photosensitive resin composition includes a photosensitive polyimide precursor, a silane coupling agent, and a nitrogen-containing heterocyclic compound, in which the structure of the silane coupling agent is represented by general formula (1): (1) in the general formula (1), R1, R2, R3 each independently represent a methoxy group, an ethyoxyl group, a methoxyethyoxyl group, an acetoxy group, a methyl group, an ethyl group, or a hydrogen atom, and R1, R2, R3 each independently represent a methoxy group, an ethyoxyl group, a methoxyethyoxyl group, an acetoxy group, a methyl group, an ethyl group, or a hydrogen atom; at least one of R1, R2 and R3 is a methoxy group, an ethyoxyl group, a methoxy ethyoxyl group and an acetoxyl group; x is an aromatic organic group with the carbon atom number of 6-50; m is an integer from 1 to 6, and n is an integer from 1 to 10; the nitrogen-containing heterocyclic ring compound is an azole compound or a purine compound; the negative photosensitive resin composition has the advantages of high sensitivity, strong adhesion to a substrate, inhibition of developing film stripping and residue defects, protection of a metal copper substrate from oxidation, and good pattern precision after curing.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology for semiconductors, specifically relating to a negative photosensitive resin composition, a method for manufacturing a cured embossed pattern, and a semiconductor device. Background Technology

[0002] Advanced packaging and system integration technologies are constantly evolving, which not only improves electrical performance but also enables diversified integration, including microsystems with various forms achieved through heterogeneous integration methods, such as 2.5D and 3D chips used in artificial intelligence, network communication, and high-performance computing. The corresponding complexity and reliability issues have become a more severe challenge. Their highly integrated packaging structures usually contain different material structures with large differences in mechanical properties, which puts higher requirements on the performance of packaging materials.

[0003] Pixel separator layers in organic electroluminescent (EL) displays, isolation and planarization layers in Mini-LEDs and Micro-LEDs, planarization layers for thin-film transistors (TFTs) in various displays, and insulating films for other peripheral components are all formed from cured films of photosensitive resin compositions patterned using photolithography. If these cured films are peeled off from adjacent components (such as other insulating layers, circuitry, or light-emitting elements), it can lead to cracks in the circuitry or damage to the components, resulting in poor light emission from the display. Therefore, high adhesion between the cured film and each component is required. In particular, Mini-LED and Micro-LED displays require high adhesion between the cured film and the metals and metal oxides contained in the circuitry and LED chips. Furthermore, excellent chemical resistance is required during display manufacturing to prevent adhesion degradation due to chemicals used in processing peripheral components. Additionally, when patterning using photosensitive resin compositions via photolithography, it is necessary to simultaneously suppress the peeling of development residues in the openings and the remaining film. On the other hand, when patterns are formed on copper using photosensitive resin compositions, discoloration due to copper corrosion has been observed, and improvements are needed in this regard.

[0004] The present invention was made in view of this actual situation, and one of its objectives is to provide a negative photosensitive resin composition that does not affect the material reliability even when in contact with different materials, i.e., no peeling occurs, and there is no residue or peeling of residual film during development, while protecting the metal interface in contact with the material from oxidation. Summary of the Invention

[0005] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0006] In a first aspect, this application provides a negative photosensitive resin composition comprising a photosensitive polyimide precursor, a silane coupling agent, and a nitrogen-containing heterocyclic compound, wherein the silane coupling agent has the structure shown in general formula (1):

[0007] (1)

[0008] Wherein, R1, R2, and R3 each independently represent methoxy, ethoxy, methoxyethoxy, acetoxy, methyl, ethyl, or hydrogen atoms, and at least one of R1, R2, and R3 is methoxy, ethoxy, methoxyethoxy, or acetoxy; X is an aromatic organic group with 6 to 50 carbon atoms; m is an integer from 1 to 6, and n is an integer from 1 to 10; the nitrogen-containing heterocyclic compound is an azole compound or a purine compound.

[0009] In some possible embodiments, in the silane coupling agent structure (1), R1, R2, and R3 each independently represent a methoxy, ethoxy, methyl, ethyl, or hydrogen atom, and at least one of R1, R2, and R3 is substituted with a methoxy or ethoxy group; X is an organic group containing substituted or unsubstituted phenyl, naphthyl, or biphenyl groups; m is an integer from 2 to 4, and n is an integer from 3 to 6.

[0010] In some possible implementations, the silane coupling agent comprises the following structure:

[0011] , ,

[0012] , ,

[0013] , .

[0014] In some possible implementations, the photosensitive polyimide precursor structure is as shown in formula (2):

[0015] (2)

[0016] In formula (2), P represents a tetravalent organic group with 6 to 50 carbon atoms, and / or, P is an aromatic group or an alicyclic aliphatic group; Q represents a divalent organic group; s represents an integer between 2 and 300; R4 can be a hydrogen atom or an organic group as shown in the following structure (3):

[0017] (3)

[0018] In equation (3), t represents an integer from 2 to 10; R5, R6, and R7 each independently represent a monovalent organic group with 2 to 10 hydrogen or carbon atoms.

[0019] In some possible embodiments, the azole nitrogen-containing heterocyclic compound includes one or more of triazole, benzotriazole, 1H-tetrazole, methyltetrazole, imidazole, benzimidazole, 2-methylimidazolium, 4-methylimidazolium, 2-ethylimidazolium, and 2-phenylimidazolium.

[0020] In some possible embodiments, the purine-type nitrogen-containing heterocyclic compound includes one or more of 9-ethyladenine, 8-aminoadenine, 1,3,7-trimethylxanthine, and 1,3-dimethylxanthine.

[0021] In some possible embodiments, the silane coupling agent is 0.1 to 10 parts by weight, and the nitrogen-containing hybrid compound is 0.1 to 10 parts by weight, based on 100 parts by weight of the photosensitive polyimide precursor.

[0022] Secondly, this application provides a method for manufacturing a solidified embossed pattern, the method comprising the following steps:

[0023] (1) A process of coating a negative photosensitive resin composition according to any embodiment of the first aspect onto a substrate to form a photosensitive resin layer on the substrate;

[0024] (2) The process of exposing the photosensitive resin layer;

[0025] (3) The process of developing the exposed photosensitive resin layer to form an embossed pattern;

[0026] (4) The process of heating the relief pattern to form a solidified relief pattern.

[0027] Thirdly, this application provides a solidified embossed pattern, which is manufactured by the method described in the second aspect.

[0028] Fourthly, this application provides a semiconductor device, including a semiconductor element and a cured film disposed on the upper part of the semiconductor element, wherein the cured film is the cured relief pattern described in the third aspect.

[0029] Beneficial effects:

[0030] 1. The photosensitive resin composition provided in this application has excellent adhesion to copper substrates, and can suppress film peeling and residue defects generated in the developing process. It also has the beneficial effect of protecting the interface of copper or copper alloy substrates from oxidation and discoloration.

[0031] 2. The π-π conjugation between the silane coupling agent and the nitrogen-containing heterocyclic compound in the photosensitive resin composition provided in this application enhances the sensitivity of the system, resulting in good pattern accuracy after curing. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0033] It should be noted that the following embodiments are examples of this application and are used only to illustrate this application, and are not intended to limit this application. Other combinations and various modifications within the scope of this application are possible without departing from the spirit or scope of this application.

[0034] The following provides a detailed description of the negative photosensitive resin composition, the method for manufacturing the cured embossed pattern, and the semiconductor device provided in this application.

[0035] <Negative Photosensitive Resin Composition>

[0036] This embodiment provides a negative photosensitive resin composition comprising a photosensitive polyimide precursor, a silane coupling agent, and a nitrogen-containing heterocyclic compound. The present invention provides a cured embossed pattern with good pattern accuracy, high resolution, suppression of residues and film peeling during development, excellent adhesion to the substrate, and prevention of oxidation and discoloration of the metal substrate.

[0037] Silane coupling agent

[0038] In order to improve the adhesion between the cured relief pattern formed by the negative photosensitive resin composition and the substrate, and to suppress residues and film peeling during development, the negative photosensitive resin composition in this embodiment contains a silane coupling agent, the structure of which is shown in general formula (1).

[0039] (1)

[0040] In general formula (1), R1, R2, and R3 each independently represent methoxy, ethoxy, methoxyethoxy, acetoxy, methyl, ethyl, or hydrogen atoms, and at least one of R1, R2, and R3 is methoxy, ethoxy, methoxyethoxy, or acetoxy; X is an aromatic organic group with 6 to 50 carbon atoms; m is an integer from 1 to 6, and n is an integer from 1 to 10.

[0041] In this embodiment, from the viewpoint of improving exposure sensitivity, X is preferably an aromatic organic group with 6 to 50 carbon atoms, more preferably an organic group containing substituted or unsubstituted phenyl, naphthyl, anthracene, biphenyl, tolyl or methoxyphenyl, and even more preferably an organic group containing substituted or unsubstituted phenyl, naphthyl and biphenyl.

[0042] The flexible, long chains of silane coupling agents readily engage in physical entanglement with the molecular chains of photosensitive polyimide resins, linking the silane coupling agent to the resin. Furthermore, the oxygen atoms in the repeating ethylene oxide units can form hydrogen bonds with nitrogen and oxygen atoms in the polyimide resin, promoting tighter physical entanglement. Additionally, the terminal amino groups and ester bonds can also form hydrogen bonds with nitrogen and oxygen atoms in the photosensitive polyimide resin, acting as a tail-end anchoring effect and further enhancing the interaction between the non-silane-substituted portion of the silane coupling agent and the photosensitive polyimide resin.

[0043] From the perspective of increasing the compatibility between silane coupling agents and photosensitive polyimide resins, increasing the number of hydrogen bond anchors, and improving the interaction force between non-silane substituted parts and photosensitive polyimide resins, m is preferably an integer from 2 to 4, and n is preferably an integer from 3 to 6.

[0044] When R1, R2, and R3, which are bonded to silicon atoms, are replaced with methoxy, ethoxy, methoxyethoxy, or acetoxy groups, they are easily hydrolyzed into active silanol groups. These active silanol groups can form covalent bonds with metal oxides and adsorb onto the metal surface. Therefore, the cured film can be tightly bonded to the metal surface, significantly improving the adhesion of the film to the copper surface and simultaneously inhibiting the peeling of residual film during development.

[0045] From the perspective of improving the activity of silanol groups, R1, R2, and R3 are preferably methoxy or ethoxy groups; from the perspective of enhancing the adhesion between the cured film and the metal surface, R1, R2, and R3 are preferably completely replaced with methoxy or ethoxy groups.

[0046] In addition, the good adhesion between this silane coupling agent and the surface of metallic copper can form a dense protective film on the surface of metallic copper, inhibiting passivation of the metal surface and improving the metal surface's ability to resist oxidation and discoloration.

[0047] Furthermore, the interaction between the silane coupling agent and the copper substrate in this embodiment can modify the copper surface to be hydrophobic, preventing residues from adhering to the opening or the interface between exposure and non-exposure during the development process, thus inhibiting residues after development.

[0048] In this embodiment, the content of the silane coupling agent in the negative photosensitive resin composition is 0.1 to 10 parts by weight relative to 100 parts by weight of the photosensitive polyimide precursor.

[0049] From the viewpoint of metal adhesion, the lower limit of the silane coupling agent content is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, relative to 100 parts by mass of the photosensitive polyimide precursor.

[0050] From the viewpoint of preventing residues from forming during development, the upper limit of the content of the silane coupling agent is preferably 8 parts by mass or less per 100 parts by mass of the photosensitive polyimide precursor, and more preferably 6 parts by mass or less.

[0051] On the other hand, this embodiment also discloses a method for preparing the silane coupling agent, including the following steps:

[0052] S1. Take raw material R1R2R3Si-(CH2) m -X-OH reacts with ethylene oxide under the action of a catalyst at a temperature of 50~80℃ and a pressure of 1~5 atm to give intermediate 1R1R2R3Si-(CH2). m -X-(O-CH2CH2)n-OH;

[0053] S2. The above intermediate 1 is reacted with phosgene or diethyl carbonate in the presence of a base at a temperature of 0-30 °C to obtain intermediate 2 R1R2R3Si-(CH2). m -X-(O-CH2CH2) n -OC(=O)-Cl or R1R2R3Si-(CH2) m -X-(O-CH2CH2) n -OC(=O)-OEt;

[0054] S3. React the above intermediate 2 with an aqueous ammonia solution or liquid ammonia at a temperature of 20~60 °C to obtain the target product R1R2R3Si-(CH2). m -X-(O-CH2CH2) n -OC(=O)-NH2.

[0055] Photosensitive polyimide precursor

[0056] In this embodiment, the photosensitive polyimide precursor is a resin component contained in a negative photosensitive resin composition. It undergoes cyclization by heating (e.g., 200 °C), thereby converting into polyimide. After exposure and development, it exhibits high pattern accuracy and resolution. The specific structure of the photosensitive polyimide precursor is shown in the following general formula (2).

[0057] (2)

[0058] In formula (2), P represents a tetravalent organic group with 6 to 50 carbon atoms, and / or P is an aromatic group or an alicyclic aliphatic group; Q represents a divalent organic group; s represents an integer between 2 and 300; R4 can be a hydrogen atom or an organic group as shown in the following structure (3).

[0059] (3)

[0060] In equation (3), t represents an integer from 2 to 10; R5, R6, and R7 each independently represent a monovalent organic group with 2 to 10 hydrogen or carbon atoms.

[0061] In general formula (2), s is an integer from 2 to 300, without any other limitation, but from the viewpoint of the photosensitivity and mechanical properties of the negative photosensitive resin composition, an integer from 5 to 200 is preferred, and an integer from 10 to 150 is more preferred. In general formula (2), the tetravalent organic group represented by P is preferably an organic group with 6 to 50 carbon atoms, which takes into account both heat resistance and photosensitivity, and is more preferably an aromatic group or an alicyclic aliphatic group in which the -COOR group and the -COOR group and the -CONH- group are adjacent to each other. Specifically, as the tetravalent organic group represented by P, organic groups with 6 to 50 carbon atoms containing an aromatic ring can be listed, such as groups having the structure shown in the following general formula (4), but are not limited to these.

[0062]

[0063] General formula (4)

[0064] In the formula, R8 can be a group composed of hydrogen atoms, fluorine atoms, hydrocarbon groups with 1 to 10 carbon atoms, and fluorinated hydrocarbon groups with 1 to 10 carbon atoms, and h is an integer from 0 to 5.

[0065] The structure of P can be one or a combination of two or more. The P-based having the structure shown in the above formula (4) is particularly preferred in terms of balancing photosensitive properties and resolution. As a P-based, from the viewpoint of pattern accuracy and resolution, the structures shown in the following formulas (4a), (4b) and (4c) are particularly preferred among the structures shown in the above formula (4).

[0066]

[0067] (4a) (4b) (4c)

[0068] In the formula, R8 can be a group composed of hydrogen atoms, fluorine atoms, hydrocarbon groups with 1 to 10 carbon atoms, and fluorinated hydrocarbon groups with 1 to 10 carbon atoms, and h is an integer from 0 to 5.

[0069] In the above general formula (2), the double chemical bond type organic group represented by Q is preferably an organic group with 6 to 50 carbons in terms of both photosensitivity and resolution, and k is an integer from 0 to 5, including but not limited to the structures listed in the following general formula (5).

[0070]

[0071] General formula (5)

[0072] Nitrogen-containing heterocyclic compounds

[0073] In this embodiment, in order to prevent substrate oxidation and suppress discoloration on the surface of metallic copper or copper alloy substrate, the negative photosensitive resin composition contains nitrogen-containing heterocyclic compounds. Examples of nitrogen-containing heterocyclic compounds in this embodiment include two types: azole compounds and purine compounds.

[0074] On the other hand, the nitrogen-containing heterocyclic compound in this embodiment has a π-electron conjugated system, which easily forms a π-π stacking effect with the aromatic ring in the silane coupling agent. This promotes the transfer of photoelectrons in the free radicals generated after the photoinitiator absorbs ultraviolet light and the initiation of double bonds in the side chain of the photosensitive polyimide precursor, thereby improving the utilization rate of the primary free radicals in the system and increasing the exposure sensitivity of the negative photosensitive resin composition.

[0075] Examples of azole compounds include triazole, benzotriazole, 1H-tetrazole, methyltetrazole, and imidazole, benzimidazole, 2-methylimidazole, 4-methylimidazole, 2-ethylimidazole, and 2-phenylimidazole.

[0076] Examples of purine compounds include: 9-ethyladenine, 8-aminoadenine, 1-benzyladenine, N,N-dimethyladenine, 9-(2-hydroxyethyl)adenine, 1,3,7-trimethylxanthine, 1,3-dimethylxanthine, 8-azaxanthine, and 8-azahypoxanthine.

[0077] Among them, benzotriazole and 8-aminoadenine are particularly preferred.

[0078] In this embodiment, the content of nitrogen-containing heterocyclic compounds in the negative photosensitive resin composition is 0.1 to 10 parts by weight relative to 100 parts by weight of photosensitive polyimide precursor.

[0079] For the purpose of preventing discoloration and corrosion of copper or copper alloys, the lower limit of the content of nitrogen-containing heterocyclic compounds is preferably 0.3 parts by mass or more relative to 100 parts by mass of photosensitive polyimide precursor.

[0080] From a sensitivity point of view, the upper limit of the content of nitrogen-containing heterocyclic compounds is preferably less than 5 parts by mass per 100 parts by mass of photosensitive polyimide precursor.

[0081] As is well known in the art, this embodiment also includes a photoinitiator and a crosslinking agent.

[0082] Photoinitiator

[0083] In this embodiment, the photoinitiator is selected from oxime ester compounds with high photosensitivity, high conversion rate and high transparency, including but not limited to sulfur-containing or other heteroatom-type oxime esters.

[0084] Specific examples of photoinitiators include: 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenyltrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxytrione-2-(o-benzoyl)oxime, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(o-benzoyl oxime), etc.

[0085] In this embodiment, the content of photoinitiator in the negative photosensitive resin composition is 0.1-25 parts by weight relative to 100 parts by weight of photosensitive polyimide precursor.

[0086] Crosslinking agent

[0087] In this embodiment, the crosslinking agent can be a crosslinking agent that can crosslink the polyimide precursor or form a crosslinking network when the embossed pattern formed by the negative photosensitive resin composition is heated and cured, which can further enhance the heat resistance and pattern accuracy of the cured film formed by the negative photosensitive resin composition.

[0088] Crosslinking agents can be listed as follows: tetraethylene glycol dimethacrylate, 2-hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, glycidyl acrylate, glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate, ethylene glycol diethyl ether methacrylate, ethylene glycol diethyl ether acrylate and polyethylene glycol methacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tri(2-hydroxyethyl)isocyanurate triacrylate and tricyclodecanedimethyl diacrylate, etc.

[0089] In this embodiment, the content of photoinitiator in the negative photosensitive resin composition is 0.1-25 parts by weight relative to 100 parts by weight of photosensitive polyimide precursor.

[0090] <Method for manufacturing solidified embossed patterns>

[0091] In this embodiment, a method for manufacturing a solidified relief pattern including the following steps (1) to (4) can be provided:

[0092] (1) A process of coating the above negative photosensitive resin composition onto a substrate to form a photosensitive resin layer on the substrate;

[0093] (2) The process of exposing the photosensitive resin layer;

[0094] (3) The process of developing the exposed photosensitive resin layer to form an embossed pattern;

[0095] (4) The process of heating the relief pattern to form a solidified relief pattern.

[0096] Some of the steps in (1) to (4) can be repeated. The following is an explanation of each step.

[0097] In one embodiment of step (1), a photosensitive resin composition is coated onto a substrate, and then dried as needed to form a photosensitive resin layer. Examples of coating methods include those traditionally used for coating photosensitive resin compositions, such as methods using spin coaters, bar coaters, scraper coaters, curtain coaters, screen printing machines, etc., and spray coating methods using spray coaters.

[0098] Examples of drying methods for photosensitive resin compositions include air drying, oven or hot plate drying, and vacuum drying. The drying of the coating film is desirable to be carried out under conditions that do not cause imidization of the photosensitive polyimide precursor in the photosensitive resin composition. Specifically, in the case of air drying or hot drying, drying can be carried out at 20–140 °C for 1–60 minutes.

[0099] In one embodiment of step (2), an exposure device such as a contact lithography machine, a projection exposure machine, or a stepper is used to expose the photosensitive resin layer formed in step (1) with or without the aid of a patterned photomask or grating, using an ultraviolet light source.

[0100] Subsequently, for purposes such as improving photosensitivity, post-exposure baking (PEB) and / or pre-development baking can be performed according to any combination of temperature and time as needed. Regarding the range of baking conditions, the temperature is preferably 40~120 °C, and the time is preferably 10~240 seconds. These can be appropriately varied according to the characteristics of the photosensitive resin composition.

[0101] In one aspect of step (3), the unexposed portions of the exposed photosensitive resin layer are developed and removed. Examples of developing methods for developing the exposed or irradiated photosensitive resin layer include developing methods using known photoresists, such as spin spraying, paddle spraying, and immersion methods with ultrasonic treatment. Furthermore, after development, baking can be performed according to any combination of temperature and time for purposes such as adjusting the shape of the relief pattern. The developing solution used in development is preferably a good solvent relative to the negative photosensitive resin composition, or a combination of a good solvent and a poor solvent. Good solvents include, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. Poor solvents include, for example, toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, and water.

[0102] When using a mixture of good and bad solvents, it is preferable to adjust the ratio of bad solvent to good solvent according to the solubility of the polymer in the photosensitive resin composition.

[0103] In one embodiment of step (4), the embossed pattern obtained by the above-described development is heated to cause the photosensitive components to evaporate and the polyimide precursor to undergo imidization, thereby transforming it into a cured embossed pattern formed of polyimide. Examples of heat curing methods include, for instance, methods based on a heating plate, methods using an oven, and methods using a temperature-programmable oven. Heating can be performed, for example, at 200–400 °C for 0.5–5 hours. The atmosphere used for heat curing can be air, or inactive gases such as nitrogen or argon.

[0104] Semiconductor Devices

[0105] One embodiment of this invention is a semiconductor device having a cured embossed pattern obtained from a photosensitive resin composition. According to one embodiment, a semiconductor device is provided having: a substrate as a semiconductor element, and a cured embossed pattern of polyimide formed on the substrate by the aforementioned cured embossed pattern manufacturing method. Another embodiment is a method for manufacturing a semiconductor device, using a semiconductor element as a substrate, and including the aforementioned cured embossed pattern manufacturing method as part of the process.

[0106] The solidified embossed pattern formed by the above-described solidified embossed pattern manufacturing method is formed in the form of a surface protective film for electronic components, an interlayer insulating film, a redistribution insulating film, and a protective film for flip-chip devices; a protective film for semiconductor devices with a bump structure, etc., and can be combined with known semiconductor device manufacturing methods to manufacture the semiconductor device of this embodiment.

[0107] In addition to being applicable to the aforementioned semiconductor devices, the negative photosensitive resin composition of this application is also used for interlayer insulation of multilayer circuits, surface layers of flexible copper-clad laminates, solder resist films, and liquid crystal alignment films.

[0108] Example

[0109] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that the embodiments are merely illustrative of the present invention and should not be construed as specific limitations thereof.

[0110] In this embodiment, the raw materials are all commercially available bulk industrial products, and the manufacturers include BASF, Wanhua Chemical, Asahikawa Chemical, Huafeng, etc.

[0111] Preparation Example A-1

[0112] Silane coupling agent A-1

[0113] S1. Take 1 mol of (EtO)2(Me)Si-(CH2)3-Ph-OH and add it to the reaction vessel. Add an appropriate amount of sodium hydroxide as a catalyst, and then pass 3 mol of ethylene oxide through it. React for 5 hours at a temperature of 60 ℃ and a pressure of 3 atm to obtain intermediate 1 (EtO)2(Me)Si-(CH2)3-Ph-(O-CH2CH2)3-OH.

[0114] S2. Add 1 mol of intermediate 1 to another reactor, add 1.2 mol of diethyl carbonate and 1.5 mol of triethylamine, and react at 20 °C for 3 hours to obtain intermediate 2 (EtO)2(Me)Si-(CH2)3-Ph-(O-CH2CH2)3-OC (=O)-OEt.

[0115] S3. Add 1 mol of intermediate 2 to the reaction vessel, add 5 mol of 25% ammonia solution, and react at 40 ℃ for 4 hours. After the reaction is completed, extract the reaction solution with ethyl acetate, wash the organic phase with water until neutral, dry it, and separate it by column chromatography to obtain the target product (EtO)2(Me)Si-(CH2)3-Ph-(O-CH2CH2)3-OC (=O)-NH2, with a yield of 90% and a purity of 98%.

[0116] Preparation Examples A-2 to A-6

[0117] The preparation methods of silane coupling agents 2-6 are the same as those in Preparation Example 1, except that the raw materials and the relative molar ratio of ethylene oxide are changed according to the corresponding target product structure. The preparation conditions and post-processing methods are the same, so they will not be described again in this embodiment. The structural formulas of the specific products silane coupling agents 1-6 are shown in Table 1.

[0118] Table 1. Structural formulas of silane coupling agents prepared in Examples 1-6

[0119] structural Preparation Example A-1 Silane coupling agent A-1 Preparation Example A-2 Silane coupling agent A-2 Preparation Example A-3 Silane coupling agent A-3 Preparation Example A-4 Silane coupling agent A-4 Preparation Example A-5 Silane coupling agent A-5 Preparation Example A-6 Silane coupling agent A-6

[0120] Preparation Example B-1

[0121] Photosensitive polyimide precursor B-1

[0122] 124.1 g of 4,4'-oxophthalic anhydride (ODPA) was added to a 3 L reactor, followed by 104.1 g of 2-hydroxyethyl methacrylate and 300 mL of γ-butyrolactone (GBL). Stirring was initiated, and then 64.5 g of pyridine and 0.2 g of hydroquinone were added. The mixture was heated to 45 °C and reacted for 4 h, followed by a further reaction at room temperature for 12 h. The system temperature was then lowered to 0 °C, and 165.9 g of dicyclohexylcarbodiimide (DCC) dissolved in 300 mL of GBL solution was added dropwise over 60 min. Immediately afterward, 72.1 g of 4,4'-diaminodiphenyl ether dissolved in 700 mL of GBL solution was added dropwise over another 60 min. After the addition was complete, the reaction was continued at 0 °C for 2 h. Finally, 24 mL of ethanol was added, and the mixture was stirred at room temperature for 1 h. The solids produced during the reaction were then filtered off. 400 mL of diluted GBL filtrate was added, and this solution was slowly added to a 3 L ethanol / water (4:1 volume ratio) mixture. The mixture was filtered again, and then washed three times with ultrapure water. The resulting wet resin polymer was vacuum dried to obtain a powdered polymer. The molecular weight of the photosensitive polyimide precursor 1 was determined by gel permeation chromatography (converted from standard polystyrene), and the weight-average molecular weight was 23400.

[0123] Preparation Example B-2

[0124] Photosensitive polyimide precursor B-2

[0125] Except that 117.7 g of 4,4'-phthalic anhydride (BPDA) was used instead of 124.1 g of 4,4'-oxobisphthalic anhydride (ODPA), the reaction was carried out in the same manner as described in Manufacturing Example 1 above, to produce photosensitive polyimide precursor 2. The molecular weight of photosensitive polyimide precursor 2 was determined by gel permeation chromatography (converted to standard polystyrene), and the weight-average molecular weight result was 22,100.

[0126] Example 1

[0127] The photosensitive polyimide precursor 1 (B-1): 100 parts, silane coupling agent (A-1): 6 parts, nitrogen-containing heterocyclic compound benzotriazole (C-1): 0.8 parts, photoinitiator 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl oxime) (D-1): 4 parts, crosslinking agent tetraethylene glycol dimethacrylate (E-1): 8 parts, are dissolved together in a mixed solvent containing 120 parts of N-methyl-2-pyrrolidone and 30 parts of ethyl lactate, totaling 150 parts (F-1). The viscosity of the resulting solution is adjusted to approximately 40 poise by further adding a small amount of the mixed solvent to prepare a negative photosensitive resin composition, and its performance is evaluated.

[0128] The preparation methods of Examples 2-8 and Comparative Examples 1-4 are the same as those of Example 1. The specific substances and mass fractions of photoinitiator, crosslinking agent and solvent are the same as those of Example 1. The only difference is that the specific substances and proportions of photosensitive polyimide precursor, silane coupling agent and nitrogen-containing heterocyclic compound are different, as shown in Table 2.

[0129] Other label definitions:

[0130] Silane coupling agent (a-7): 3-Ureapropyltriethoxysilane

[0131] Nitrogen-containing heterocyclic compounds (C-2): 2-methylimidazole

[0132] Nitrogen-containing heterocyclic compounds (C-3): 8-aminoadenine

[0133] Nitrogen-containing heterocyclic compounds (C-4): 1,3-dimethylxanthine

[0134] Table 2

[0135] Photosensitive polyimide precursor Silane coupling agent Nitrogen-containing heterocyclic compounds Example 1 B-1100 copies A-16 copies C-10.8 copies Example 2 B-1100 copies A-26 copies C-10.8 copies Example 3 B-1100 copies A-36 copies C-10.8 copies Example 4 B-1100 copies A-46 copies C-10.8 copies Example 5 B-1100 copies A-56 copies C-10.8 copies Example 6 B-1100 copies A-66 copies C-10.8 copies Example 7 B-2100 copies A-56 copies C-10.8 copies Example 8 B-2100 copies A-56 copies C-20.8 copies Example 9 B-2100 copies A-56 copies C-30.8 copies Example 10 B-2100 copies A-56 copies C-40.8 copies Example 11 B-1100 copies A-51 copies C-25 copies Example 12 B-1100 copies A-59 copies C-27 copies Example 13 B-1100 copies A-512 copies C-212 copies Comparative Example 1 B-1100 copies a-76 copies C-20.8 copies Comparative Example 2 B-1100 copies / C-20.8 copies Comparative Example 3 B-1100 copies A-51 copies / Comparative Example 4 B-1100 copies / /

[0136] The physical properties of the negative photosensitive resin composition were determined and evaluated according to the following methods.

[0137] Sensitivity evaluation of negative photosensitive resin compositions

[0138] The optimal exposure Eop (mJ / cm²) for obtaining LS patterns with a spacing of 10 μm and a pitch of 20 μm was determined by observing the LS patterns using an electron microscope. 2 ).

[0139] Precision evaluation of polyimide patterns

[0140] A photosensitive resin composition was spin-coated onto a 6-inch silicon wafer and dried to form a 10 μm thick coating. This coating was then developed using a scale line with a test pattern via an i-ray stepper NSR1755i7B (manufactured by NIKON CORPORATION). Next, the coating formed on the wafer was developed by spray using cyclopentanone with a developer (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.), and rinsed with propylene glycol methyl ether acetate to obtain the pattern.

[0141] For the patterned wafer, a temperature-programmed curing oven (VF-2000 type, manufactured by Koyo Lindberg Ltd.) was used to heat-treat at 230 °C for 2 hours under a nitrogen atmosphere, thereby obtaining a 7 μm thick polyimide pattern on the silicon wafer.

[0142] The accuracy of polyimide patterns is evaluated based on the following benchmarks.

[0143] "Good": The bottom edge of the pattern cross section does not curl, and there will be no undercut, swelling or bridging. The pattern has an aspect ratio of 1 or higher and the pattern shape will not change during heat curing.

[0144] "Poor": A pattern that does not meet at least one of the above "Good" criteria.

[0145] Evaluation of the adhesion of polyimide patterns

[0146] A negative-type photosensitive resin composition was spin-coated onto a copper substrate and dried to form a 10 μm thick coating as the photosensitive resin layer. Then, a temperature-programmed curing oven was used to heat-treat (cur) the coating at 200 °C for 2 hours under a nitrogen atmosphere to obtain a 6.5 μm thick polyimide coating. Film thickness was measured using a laser confocal microscope. For the cured film, the adhesion characteristics between the metal material (copper substrate) and the heat-resistant resin (polyimide coating) were evaluated based on the cross-cut method of GB / T 9286-2021, according to the following criteria:

[0147] 5B: The polyimide coating bonded to the substrate has a grid number of 100;

[0148] 4B: The polyimide coating bonded to the substrate has a grid number of 95~99;

[0149] 3B: The polyimide coating bonded to the substrate has a grid number of 85~94;

[0150] 2B: The number of grids in the polyimide coating bonded to the substrate is 65~84;

[0151] 1B: The number of grids in the polyimide coating bonded to the substrate is 35~64;

[0152] 0B: The number of grids in the polyimide coating bonded to the substrate is less than 35.

[0153] Evaluation of peeling degree during development

[0154] Observe whether the developed films obtained in each case peel off during development. As an indicator of peeling during development, calculate the area of ​​the peeled film relative to the patterned residual film. The area of ​​the peeled film is judged according to the following criteria:

[0155] A: The area of ​​the peeling film is less than 1%;

[0156] B: The area of ​​the peeling film is more than 1% but less than 3%;

[0157] C: The area of ​​the peeling film is more than 3% but less than 5%;

[0158] D: The area of ​​the peeling film is more than 5% but less than 20%;

[0159] E: The area of ​​the peeling film is more than 20% but less than 100%.

[0160] Evaluation of residual levels during development

[0161] Observe the analytical patterns of the developed films obtained in each case. As an indicator of development residue, observe the presence or absence of residue in the 20 μm line and spatial pattern, and calculate the area occupied by the residue at the opening. The evaluation criteria for residue area are as follows:

[0162] A: The area of ​​residue is less than 1%;

[0163] B: The area of ​​residue is more than 1% and less than 3%;

[0164] C: The area of ​​residue is more than 3% and less than 5%;

[0165] D: The area of ​​residue is more than 5% and less than 20%;

[0166] E: The area of ​​residue is more than 20% but less than 100%.

[0167] Evaluation of the degree of oxidation on the substrate surface

[0168] Observe the cured film of the negative photosensitive resin composition. Visually observe the color of the copper surface in the unexposed area. Mark no color change as ○, partial color change as ×, and complete color change as ××.

[0169] Table 3 Evaluation Results of Examples and Comparative Examples

[0170] <![CDATA[Sensitivity (mJ / cm 2 ).]]> Pattern precision Adhesion Degree of peeling during development Residual degree during development Degree of oxidation on substrate surface Example 1 285 good 5B A A ○ Example 2 285 good 4B B A ○ Example 3 285 good 5B A A ○ Example 4 285 good 4B B B ○ Example 5 285 good 5B A A ○ Example 6 285 good 5B A A ○ Example 7 285 good 5B A B ○ Example 8 285 good 5B A A ○ Example 9 285 good 4B A A ○ Example 10 285 good 5B B A ○ Example 11 285 good 3B C B ○ Example 12 295 good 5B A C ○ Example 13 295 Poor 4B B E ○ Comparative Example 1 315 Poor 1B D C × Comparative Example 2 315 Poor 0B E D × Comparative Example 3 325 Poor 3B C C × Comparative Example 4 330 Poor 0B E C ××

[0171] It should be noted that, based on the explanations and descriptions in the foregoing specification, those skilled in the art can make changes and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some equivalent modifications and alterations to the present invention should also be within the scope of protection of the claims of the present invention. Furthermore, although some specific terms are used in this specification, these terms are only for convenience of explanation and do not constitute any limitation on the invention.

Claims

1. A negative photosensitive resin composition, characterized in that, It comprises a photosensitive polyimide precursor, a silane coupling agent, and a nitrogen-containing heterocyclic compound, wherein the structure of the silane coupling agent is shown in general formula (1): (1) Wherein, R1, R2, and R3 each independently represent methoxy, ethoxy, methoxyethoxy, acetoxy, methyl, ethyl, or hydrogen atoms, and at least one of R1, R2, and R3 is methoxy, ethoxy, methoxyethoxy, or acetoxy; X is an aromatic organic group with 6 to 50 carbon atoms; m is an integer from 1 to 6, and n is an integer from 1 to 10; the nitrogen-containing heterocyclic compound is an azole compound or a purine compound.

2. The negative photosensitive resin composition according to claim 1, characterized in that, In the silane coupling agent structure (1), R1, R2, and R3 each independently represent methoxy, ethoxy, methyl, ethyl, or hydrogen atoms, and at least one of R1, R2, and R3 is substituted with methoxy or ethoxy; X is an organic group containing substituted or unsubstituted phenyl, naphthyl, or biphenyl groups; m is an integer from 2 to 4, and n is an integer from 3 to 6.

3. The negative photosensitive resin composition according to claim 2, characterized in that, The silane coupling agent comprises the following structure: 、 、 、 、 、 。 4. The negative photosensitive resin composition according to claim 1, characterized in that, The structure of the photosensitive polyimide precursor is shown in formula (2): （2） In formula (2), P represents a tetravalent organic group with 6 to 50 carbon atoms, and / or, P is an aromatic group or an alicyclic aliphatic group; Q represents a divalent organic group; s represents an integer between 2 and 300; R4 can be a hydrogen atom or an organic group as shown in the following structure (3): （3） In equation (3), t represents an integer from 2 to 10; R5, R6, and R7 each independently represent a monovalent organic group with 2 to 10 hydrogen or carbon atoms.

5. The negative photosensitive resin composition according to claim 1, characterized in that, The nitrogen-containing heterocyclic azole compounds include one or more of the following: triazole, benzotriazole, 1H-tetrazole, methyltetrazole, imidazole, benzimidazole, 2-methylimidazolium, 4-methylimidazolium, 2-ethylimidazolium, and 2-phenylimidazolium.

6. The negative photosensitive resin composition according to claim 1, characterized in that, The nitrogen-containing heterocyclic purine compounds include one or more of 9-ethyladenine, 8-aminoadenine, 1,3,7-trimethylxanthine, and 1,3-dimethylxanthine.

7. The negative photosensitive resin composition according to claim 1, characterized in that, Based on 100 parts by weight of the photosensitive polyimide precursor, the silane coupling agent comprises 0.1 to 10 parts by weight, and the nitrogen-containing hybrid compound comprises 0.1 to 10 parts by weight.

8. A method for manufacturing a solidified relief pattern, characterized in that, The manufacturing method includes the following steps: (1) The process of coating the negative photosensitive resin composition of any one of claims 1 to 7 onto a substrate to form a photosensitive resin layer on the substrate; (2) The process of exposing the photosensitive resin layer; (3) The process of developing the exposed photosensitive resin layer to form an embossed pattern; (4) The process of heating the relief pattern to form a solidified relief pattern.

9. A type of solidified relief pattern, characterized in that, The solidified relief pattern is manufactured by the method described in claim 8.

10. A semiconductor device, characterized in that, It includes a semiconductor element and a cured film disposed on the upper part of the semiconductor element, wherein the cured film is the cured relief pattern as described in claim 9.

Images