Photosensitive resin, photosensitive resin composition, cured product, pattern forming method, and integrated circuit device

Abstract

The present application relates to a photosensitive resin, a photosensitive resin composition, a cured product, a pattern forming method, and an integrated circuit device. The photosensitive resin of the present application includes, at least in the main chain, a structural unit derived from tetracarboxylic dianhydride represented by the following general formula (1) and a structural unit derived from diamine represented by the following general formula (2): In the general formula (1), X represents a tetravalent organic group; in the general formula (2), Y1 represents a divalent organic group having one or more azobenzene compounds. The photosensitive resin composition of the present application contains the photosensitive resin. The cured product of the present application is formed by the photosensitive resin composition of the present application. The pattern forming method of the present application uses the photosensitive resin composition of the present application. The integrated circuit device of the present application is configured with a layer of the cured product of the present application.

Description

Technical Field

[0001] The present application relates to the fields of photosensitive resins, photosensitive resin compositions, cured products, pattern forming methods, and integrated circuit devices, and in particular to a photosensitive resin, a positive photosensitive resin composition containing the photosensitive resin, a cured product formed from the positive photosensitive resin composition, a pattern forming method using the positive photosensitive resin composition, and an integrated circuit device having a layer provided with the cured product. Background Art

[0002] With the miniaturization and increasing performance of consumer electronics, especially tablets, laptops, digital cameras, mobile phones, wearable electronic devices, and virtual reality devices, the demand for higher integration and durability of integrated circuit (IC) devices is increasing. Generally, in integrated circuit (IC) devices, the application of protective films and insulating films for various components, especially stress buffer coatings and insulating films for redistribution layers (RDLs) of semiconductor components, generally requires the use of polymer materials with low thermal expansion coefficients, good thermal stability, and excellent dimensional and chemical stability.

[0003] Typically, resins such as polyimide (PI) have excellent overall properties that can meet the performance requirements of the aforementioned integrated circuit (IC) device field. Therefore, they have been used as various protective films and insulating films in integrated circuit (IC) devices for many years. Traditionally, the aforementioned integrated circuit (IC) device field typically uses non-photosensitive polyimide, with conventional photoresists used for process operations such as patterning and through-hole formation. This process is cumbersome, and due to the repeated use of wet etching processes, the photolithographic pattern resolution is low and the sidewall profile is poor. To this end, people have developed photosensitive resins such as photosensitive polyimide (PSPI) resin.

[0004] Photosensitive polyimide (PSPI) generally refers to a class of polyimide or polyimide precursor (polyamic acid, polyamic acid ester, polyisoimide, etc.) materials that are sensitive to light sources such as ultraviolet (UV), X-rays, electron beams or ion beams. The PSPI resin composition can be used with traditional photolithography processes for mapping, through-hole processing, and other process operations, thereby directly transferring the pattern on the mask to the substrate. After post-heat curing, the PSPI cured film can be retained inside the device as an insulating layer. Therefore, the PSPI resin composition can replace the non-photosensitive polyimide resin composition interlayer dielectric material and ordinary photoresist in the traditional integrated circuit manufacturing process, thereby greatly simplifying the manufacturing process of integrated circuits, such as Figure 1 As shown in .

[0005] Based on the properties of the image after molding, PSPI resin compositions are divided into two categories: positive-type PSPI resin compositions and negative-type PSPI resin compositions. Prior art negative-type PSPI resin compositions typically include a precursor of a resin such as PSPI. These negative-type PSPI resin compositions are typically cured by a heat treatment to cyclize the precursor of the resin, such as PSPI. This heat treatment typically requires temperatures exceeding 300°C (often up to 350°C), which can easily cause thermal damage to semiconductor devices. This has been studied in the prior art.

[0006] For example, Patent Document 1 has proposed a low-temperature curable negative-type PSPI resin composition, but it requires multiple heating treatments and a complicated development process. In addition, the PSPI resin itself does not contain photosensitive groups and has insufficient photosensitivity.

[0007] Therefore, the research on positive PSPI resin composition has become a hot topic. The working principle of positive PSPI resin composition is as follows: the positive PSPI resin composition is evenly coated on the substrate and dried; a mask with a pattern is placed between the positive PSPI resin composition and the light source; during exposure, the part not blocked by the mask plate is dissolved, and the part blocked by the mask plate is not dissolved, such as Figure 2 As shown in .

[0008] For example, Patent Document 2 proposes a polyimide resin for use in positive-type PSPI resin compositions. This resin is obtained by heating polyamic acid or subjecting it to chemical treatment with an acid or alkali, resulting in dehydration and ring closure. This polyimide resin has an imidization rate of 85% or higher, minimizing film shrinkage caused by dehydration and ring closure during imidization by heating, thereby suppressing warping. However, this polyimide resin itself lacks photosensitive groups, resulting in insufficient photosensitivity and poor solubility after exposure.

[0009] In view of the above, the present application aims to provide a photosensitive resin having a photosensitive group, so that the photosensitive resin can have better photosensitivity than the prior art and improved solubility after exposure. When a photosensitive resin composition containing the photosensitive resin is used as a positive photosensitive resin composition, the curing temperature during curing is low and there is no obvious volume shrinkage, and the desired cured product pattern can be formed with a higher resolution.

[0010] Patent Literature

[0011] Patent Document 1: CN101055420A

[0012] Patent Document 2: CN104662475A Summary of the Invention

[0013] In view of this, a photosensitive resin is proposed. The photosensitive resin has excellent photosensitivity, exhibits excellent insolubility before exposure, and exhibits improved solubility after exposure. Therefore, the photosensitive resin composition using the photosensitive resin has a low curing temperature and no significant volume shrinkage during curing, and can produce a cured product with excellent photosensitivity, improved solubility after exposure, and high resolution. Furthermore, the cured product is given hydrophobicity, and even reduces chemical damage to the substrate.

[0014] A photosensitive resin composition is also proposed, which has a low curing temperature and no obvious volume shrinkage during curing, and can produce a cured product with excellent photosensitivity, improved solubility after exposure, and high resolution. Furthermore, the cured product is given hydrophobicity and even has reduced chemical damage to the substrate.

[0015] A cured product is also proposed, which has excellent photosensitivity, exhibits improved solubility after exposure, has high resolution, is hydrophobic, and is less chemically damaging to the substrate.

[0016] A pattern forming method has also been proposed, which has minimal thermal damage to a substrate and can efficiently form a fine, high-resolution cured product pattern. Furthermore, the resulting cured product pattern is hydrophobic and has minimal chemical damage to the substrate.

[0017] There is also proposed an integrated circuit device which is capable of achieving both excellent high integration and excellent durability in use due to the provision of a layer of the cured product.

[0018] In a first aspect, an embodiment of the present application provides a photosensitive resin comprising, at least in its main chain, a structural unit derived from tetracarboxylic dianhydride represented by the following general formula (1) and a structural unit derived from diamine represented by the following general formula (2):

[0019]

[0020] In the general formula (1), X represents a tetravalent organic group; and in the general formula (2), Y1 represents a divalent organic group having one or more azobenzene compounds.

[0021] In this case, the photosensitive resin of the present application has excellent photosensitivity, and exhibits excellent insolubility before exposure and improved solubility after exposure. Therefore, the photosensitive resin composition using it has a low curing temperature and no obvious volume shrinkage during curing, and can obtain a cured product with excellent photosensitivity, improved solubility after exposure, and high resolution.

[0022] According to the first aspect, in a first possible implementation of the photosensitive resin, X represents a tetravalent organic group having 1 to 4 ring structures of at least one selected from an aromatic ring, a 4 to 15-membered aliphatic ring, and a 4 to 15-membered heterocyclic ring.

[0023] In this case, the photosensitive resin of the present application has better photosensitivity, exhibits better insolubility before exposure, and has improved mechanical properties.

[0024] According to the first aspect, in a first possible implementation of the photosensitive resin, the photosensitive resin includes at least in the main chain a structural unit represented by the following general formula (A):

[0025]

[0026] In the general formula (A), X is the same as in the general formula (1), and Y1 is the same as in the general formula (2).

[0027] In this case, the photosensitive resin of the present application has better photosensitivity, and exhibits better insolubility before exposure and improved solubility after exposure, and also has excellent mechanical properties. Therefore, the photosensitive resin composition using it has a low curing temperature and no obvious volume shrinkage during curing, and can obtain a cured product with better photosensitivity, improved solubility after exposure, higher resolution, and excellent mechanical properties.

[0028] According to the first aspect, in any one of the first to third possible implementations of the photosensitive resin, the azobenzene compound is a compound having a structure represented by the following general formula (3):

[0029]

[0030] In the general formula (3), R1 and R2 are each selected from any one of a hydrogen atom, a C1-40 alkyl group, a C2-40 alkenyl group, a C1-40 alkoxy group, a C2-40 alkenyloxy group, a C2-40 epoxy group, a C6-40 aryl group, a C8-40 aralkenyl group, a C8-40 aralkynyl group, a C7-40 aromatic ring group, a C1-40 halogenated alkyl group, a C1-40 halogenated alkoxy group, a C2-40 halogenated alkenyl group, a C2-40 halogenated alkynyl group, a C2-40 halogenated alkenyloxy group, a C2-40 halogenated epoxy group, a C6-40 halogenated aryl group, a C8-40 halogenated aralkenyl group, and a C7-40 halogenated aromatic ring group.

[0031] In this case, the photosensitive resin of the present application is more excellent in photosensitivity, exhibits more excellent insolubility before exposure and exhibits more improved solubility after exposure, and is easily available.

[0032] According to the first aspect, in a fourth possible implementation of the photosensitive resin, Y1 represents a divalent organic group represented by the following general formula (2-1):

[0033]

[0034] In the general formula (2-1), R1 and R2 are each selected from any one of a hydrogen atom, a C1-40 alkyl group, a C2-40 alkenyl group, a C1-40 alkoxy group, a C2-40 alkenyloxy group, a C2-40 epoxy group, a C6-40 aryl group, a C8-40 aralkenyl group, a C8-40 aralkynyl group, a C7-40 aromatic ring group, a C1-40 halogenated alkyl group, a C1-40 halogenated alkoxy group, a C2-40 halogenated alkenyl group, a C2-40 halogenated alkynyl group, a C2-40 halogenated alkenyloxy group, a C2-40 halogenated epoxy group, a C6-40 halogenated aryl group, a C8-40 halogenated aralkenyl group, and a C7-40 halogenated aromatic ring group.

[0035] In this case, the photosensitive resin of the present application is further excellent in photosensitivity, exhibits further excellent insolubility before exposure and further improved solubility after exposure, and is more easily available.

[0036] According to the first aspect, in any one of the first to third possible implementations of the photosensitive resin, in the photosensitive resin, the content of the diamine-derived structural unit represented by general formula (2) is 10 mol% or more relative to 100 mol% of all diamine-derived structural units.

[0037] In this case, the photosensitive resin of the present application is more excellent in photosensitivity, and exhibits more excellent insolubility before exposure and more improved solubility after exposure.

[0038] According to the first aspect, in any one of the first to third possible implementations of the photosensitive resin, the photosensitive resin further includes a diamine-derived structural unit represented by the following general formula (4):

[0039]

[0040] In the general formula (4), Y2 represents a divalent organic group having a group derived from a quinonediazide compound and 1 to 4 aromatic rings.

[0041] In this case, the photosensitive resin of the present application has particularly excellent photosensitivity, exhibits excellent insolubility and hydrophobicity before exposure, and exhibits particularly improved solubility after exposure. Therefore, even if the photosensitive resin composition contains a small amount (or even no) of photosensitizer, it can produce a cured product with excellent photosensitivity, excellent insolubility and hydrophobicity before exposure, improved solubility after exposure, and high resolution, thereby reducing chemical damage to the substrate.

[0042] According to the first aspect, in a seventh possible implementation of the photosensitive resin, the photosensitive resin further includes a structural unit represented by the following general formula (B):

[0043]

[0044] In the general formula (B), X is the same as in the general formula (1), and Y2 is the same as in the general formula (4).

[0045] In this case, the photosensitive resin of the present application has particularly excellent photosensitivity, exhibits superior insolubility and improved hydrophobicity before exposure, exhibits particularly improved solubility after exposure, and also has excellent mechanical properties. Therefore, even if the photosensitive resin composition contains a small amount (or even no) of photosensitizer, it can produce a cured product with excellent photosensitivity, improved solubility after exposure, high resolution, excellent hydrophobicity, and excellent mechanical properties.

[0046] According to the first aspect, in a seventh possible implementation of the photosensitive resin, in the photosensitive resin, the molar ratio of the diamine-derived structural unit represented by the general formula (2) to the diamine-derived structural unit represented by the general formula (4) is 2:8 to 9:1.

[0047] In this case, the photosensitive resin of the present application has particularly excellent photosensitivity, exhibits superior insolubility and improved hydrophobicity before exposure, and exhibits significantly improved solubility after exposure. Therefore, even if the photosensitive resin composition contains a small amount (or even no) of photosensitizer, it can produce a cured product with superior photosensitivity, improved solubility after exposure, higher resolution, and superior hydrophobicity.

[0048] According to the first aspect, in a seventh possible implementation of the photosensitive resin, the quinonediazide compound is a compound having a structure represented by the following general formula (5):

[0049]

[0050] In the general formula (5), R3 is any one selected from a chlorine atom, a hydroxyl group, a C1-40 alkyl group, a C2-40 alkenyl group, a C1-40 alkoxy group, a C2-40 alkenyloxy group, a C2-40 epoxy group, a C6-40 aryl group, a C8-40 aralkenyl group, a C8-40 aralkynyl group, a C7-40 aromatic ring group, a C1-40 halogenated alkyl group, a C1-40 halogenated alkoxy group, a C2-40 halogenated alkenyl group, a C2-40 halogenated alkynyl group, a C2-40 halogenated alkenyloxy group, a C2-40 halogenated epoxy group, a C6-40 halogenated aryl group, a C8-40 halogenated aralkenyl group, and a C7-40 halogenated aromatic ring group.

[0051] In this case, the photosensitivity of the photosensitive resin of the present application is particularly excellent, and it exhibits better insolubility and better hydrophobicity before exposure, and exhibits particularly improved solubility after exposure. Even if the photosensitive resin composition using it contains a small amount (or even no) of photosensitizer, it can obtain a cured product with better photosensitivity, better solubility after exposure, higher resolution, and better hydrophobicity; and the photosensitive resin of the present application is easier to obtain.

[0052] In a second aspect, an embodiment of the present application provides a photosensitive resin composition, comprising a photosensitive resin according to any one of the first to tenth possible implementations of the first aspect, a solvent, and an optional photosensitizer.

[0053] In this case, the photosensitive resin composition of the present application has a low curing temperature and no obvious volume shrinkage during curing, and can obtain a cured product with excellent photosensitivity, improved solubility after exposure, and high resolution. Furthermore, it also imparts hydrophobicity to the cured product and even reduces chemical damage to the substrate.

[0054] According to the second aspect, in a first possible implementation of the photosensitive resin composition, when the photosensitive resin comprises the diamine-derived structural unit represented by the general formula (4), the photosensitive resin composition does not comprise a photosensitizer.

[0055] In this case, the photosensitive resin composition of the present application has a low curing temperature and no obvious volume shrinkage during curing, and even without containing a photosensitizer, a cured product with excellent photosensitivity, improved solubility after exposure, high resolution, and excellent hydrophobicity can be obtained, further reducing chemical damage to the substrate.

[0056] According to the second aspect, in a first possible implementation of the photosensitive resin composition, when the photosensitive resin does not contain the structural unit derived from diamine represented by the general formula (4), the content of the photosensitive agent is 5 to 30% by mass relative to the total mass of the photosensitive resin composition.

[0057] In this case, the photosensitive resin composition of the present application has a low curing temperature and no obvious volume shrinkage during curing, and even if it contains a small amount of photosensitizer, it can obtain a cured product with better photosensitivity, improved solubility after exposure, and higher resolution, and reduces chemical damage to the substrate.

[0058] According to the second aspect, in any one of the first to third possible implementations of the photosensitive resin composition, the photosensitive resin composition includes a cross-linking agent.

[0059] In this case, the insolubility of the cured product obtained from the photosensitive resin composition of the present application before exposure is further improved, and the warpage resistance of the photosensitive resin composition after curing is further improved.

[0060] In a third aspect, an embodiment of the present application provides a cured product formed by curing the photosensitive resin composition according to any one of the first to third possible implementations of the second aspect.

[0061] In this case, the cured product of the present application has excellent photosensitivity, exhibits improved solubility after exposure, has high resolution, is hydrophobic, and has little chemical damage to the substrate.

[0062] In a fourth aspect, an embodiment of the present application provides a pattern forming method, comprising the following steps: (1) coating a photosensitive resin composition according to any one of the first to third possible implementation methods of the second aspect on a substrate, and curing the composition to form a cured product; (2) exposing the formed cured product through a mask; and (3) developing the cured product using a developer.

[0063] In this case, the pattern forming method of the present application causes little thermal damage to the substrate and can efficiently form a fine, high-resolution cured pattern. Furthermore, the obtained cured pattern is hydrophobic and causes little chemical damage to the substrate.

[0064] In a fifth aspect, an embodiment of the present application provides an integrated circuit device configured with a layer of the cured material according to the third aspect.

[0065] In this case, the integrated circuit device of the present application can form a cured layer that has excellent photosensitivity, improved solubility after exposure, high resolution, and is hydrophobic and even has little chemical damage to the substrate, thereby achieving both excellent high integration and excellent durability.

[0066] These and other aspects of the present application will become more readily apparent from the following description of the embodiment(s). BRIEF DESCRIPTION OF THE DRAWINGS

[0067] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate exemplary embodiments, features, and aspects of the application and, together with the description, serve to explain the principles of the application.

[0068] Figure 1 An exemplary application of the photosensitive polyimide resin composition in an integrated circuit is shown.

[0069] Figure 2 The patterning process of the positive photosensitive polyimide resin composition is shown.

[0070] Figure 3 The diagram shows the changes in the molecular chain of an example of the photosensitive resin of the present application before and after exposure (a group derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride is used as X in the general formula (1), a group derived from p-aminoazobenzene is used as Y1 in the general formula (2), and R is a group derived from a quinonediazide compound). DETAILED DESCRIPTION

[0071] Various exemplary embodiments, features, and aspects of the present application will be described in detail below with reference to the accompanying drawings. The same reference numerals in the accompanying drawings represent elements with the same or similar functions. Although various aspects of the embodiments are shown in the accompanying drawings, the drawings are not necessarily drawn to scale unless otherwise indicated.

[0072] The word “exemplary” is used exclusively herein to mean “serving as an example, example, or illustration.” Any embodiment described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over other embodiments.

[0073] In addition, numerous specific details are provided in the detailed description below to better illustrate the present application. Those skilled in the art will appreciate that the present application can be practiced without certain specific details. In some instances, methods, means, components, and circuits well known to those skilled in the art are not described in detail in order to highlight the main purpose of the present application.

[0074] <First Aspect>

[0075] In order to solve the above technical problems, the present application provides a photosensitive resin, which includes at least in the main chain a structural unit derived from tetracarboxylic dianhydride represented by the following general formula (1) and a structural unit derived from diamine represented by the following general formula (2):

[0076]

[0077] In the general formula (1), X represents a tetravalent organic group; and in the general formula (2), Y1 represents a divalent organic group having one or more azobenzene compounds.

[0078] Specifically, the photosensitive resin of the present application has excellent photosensitivity due to the simultaneous presence of a structural unit derived from tetracarboxylic dianhydride represented by general formula (1) and a structural unit derived from a diamine represented by general formula (2). Furthermore, the resin exhibits excellent insolubility before exposure and improved solubility after exposure. Therefore, a photosensitive resin composition using the photosensitive resin of the present application can be cured at a low temperature without significant volume shrinkage, and can produce a cured product with excellent photosensitivity, improved solubility after exposure, and high resolution.

[0079] The composition of the photosensitive resin of the present application will be described in detail below.

[0080] (Structural unit derived from tetracarboxylic dianhydride)

[0081] In the present application, the photosensitive resin contains a structural unit derived from tetracarboxylic dianhydride represented by the following general formula (1) at least in the main chain:

[0082]

[0083] In the general formula (1), X represents a tetravalent organic group and is not particularly limited as long as it is a tetravalent organic group.

[0084] In some preferred embodiments, from the perspective of improving the photosensitivity of the photosensitive resin, exhibiting better insolubility before exposure, and improving mechanical properties, X preferably represents a tetravalent organic group having 1 to 4 cyclic structures of at least one selected from an aromatic ring, a 4-15-membered aliphatic ring, and a 4-15-membered heterocyclic ring. From the perspective of more advantageously achieving the above effects, X more preferably represents a tetravalent organic group having 1 to 4 cyclic structures of at least one selected from an aromatic ring, a 4-8-membered aliphatic ring, and a 4-8-membered heterocyclic ring. X can be a single tetravalent organic group or a combination of two or more tetravalent organic groups.

[0085] In the present application, the term "heterocycle" refers to a cyclic structure obtained by replacing at least one carbon atom of an aliphatic ring with a heteroatom, wherein the heteroatom is at least one of an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. In addition, one or more hydrogen atoms on each of the aromatic ring, the aliphatic ring, and the heterocycle may be replaced by any substituent, such as an alkyl group, an alkoxy group, an epoxy group, an aryl group, an aromatic ring oxygen group, a haloalkyl group, a haloalkoxy group, a haloepoxy group, a haloaryl group, a haloaromatic ring oxygen group, a sulfone group, an ester group, a ketone group, a halogen atom (e.g., a chlorine atom, a bromine atom, an iodine atom), etc.

[0086] In some specific embodiments, examples of tetracarboxylic dianhydrides forming the structural unit represented by general formula (1) include, but are not limited to: pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride. Acid dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-7,8,9,10-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane -1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, norbornane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-3,4,8,9-tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3 '-diphenylsulfone tetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenylether tetracarboxylic dianhydride, 2,2',3,3'-diphenylether tetracarboxylic dianhydride, 2,3,3',4'-diphenylether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, ethylene glycol bis(dehydrated trimellitate), and 5-(2,5-dioxotetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

[0087] In some preferred embodiments, from the viewpoint of further advantageously achieving the effects of the present application, the photosensitive resin of the present application necessarily contains a structural unit represented by the general formula (1) in which X represents a tetravalent organic group having 1 to 4 aromatic rings. In this case, the content of the structural unit represented by the general formula (1) in which X represents a tetravalent organic group having 1 to 4 aromatic rings is preferably 50 mol% or more, more preferably 75 mol% or more, further preferably 90 mol% or more, and most preferably 100 mol% relative to 100 mol% of all the structural units represented by the general formula (1). Here, "100 mol%" means that in the general formula (1), X represents only a tetravalent organic group having 1 to 4 aromatic rings.

[0088] (Structural unit derived from diamine)

[0089] In the present application, the photosensitive resin contains at least a diamine-derived structural unit represented by the following general formula (2) in the main chain:

[0090]

[0091] In the general formula (2), Y1 represents a divalent organic group having one or more divalent organic groups derived from an azobenzene compound, and preferably represents a divalent organic group having one divalent organic group derived from an azobenzene compound.

[0092] When the photosensitive resin of the present application contains a diamine-derived structural unit represented by general formula (2), the photosensitivity of the photosensitive resin of the present application is enhanced; at the same time, before exposure, the photosensitive resin of the present application is in an insoluble state due to its own rigidity and strong interaction between molecular segments, and the azobenzene group usually presents a thermodynamically stable trans configuration; after exposure occurs, the azobenzene structure in the exposed area undergoes cis-trans isomerization (such as Figure 3 As shown), resin T g (glass transition temperature) is significantly reduced, which weakens the rigidity of the molecular chain, increases the distance between the molecular chains, weakens the interaction force, and thus improves the solubility.

[0093] In some specific embodiments, from the perspective of more advantageously achieving the technical effects of the present application and improving the mechanical properties of the photosensitive resin, the diamine-derived structural unit represented by general formula (2) is preferably present in the form of a structural unit represented by the following general formula (A), that is, the photosensitive resin of the present application preferably contains the structural unit represented by the following general formula (A) in at least the main chain:

[0094]

[0095] In the general formula (A), X is the same as in the general formula (1), and Y1 is the same as in the general formula (2).

[0096] In some preferred embodiments, from the perspective of more advantageously achieving the technical effects of the present application and easily obtaining the resin, in Y1, the azobenzene compound is preferably a compound having a structure represented by the following general formula (3):

[0097]

[0098] In the general formula (3), R1 and R2 are each selected from any one of a hydrogen atom, a C1-40 alkyl group, a C2-40 alkenyl group, a C1-40 alkoxy group, a C2-40 alkenyloxy group, a C2-40 epoxy group, a C6-40 aryl group, a C8-40 aralkenyl group, a C8-40 aralkynyl group, a C7-40 aromatic ring group, a C1-40 halogenated alkyl group, a C1-40 halogenated alkoxy group, a C2-40 halogenated alkenyl group, a C2-40 halogenated alkynyl group, a C2-40 halogenated alkenyloxy group, a C2-40 halogenated epoxy group, a C6-40 halogenated aryl group, a C8-40 halogenated aralkenyl group, and a C7-40 halogenated aromatic ring group.

[0099] In some preferred embodiments, from the perspective of further advantageously achieving the technical effects of the present application and making it easier to obtain the resin, Y1 preferably represents a divalent organic group represented by the following general formula (2-1), and more preferably represents a divalent organic group represented by the following general formula (2-2):

[0100]

[0101] In the general formula (2-1) and the general formula (2-2), R1 and R2 are each selected from a hydrogen atom, a C1-40 alkyl group, a C2-40 alkenyl group, a C1-40 alkoxy group, a C2-40 alkenyloxy group, a C2-40 epoxy group, a C6-40 aryl group, a C8-40 aralkenyl group, a C8-40 aralkynyl group, a C7-40 aromatic ring group, a C1-40 halogenated alkyl group, a C1-40 halogenated alkoxy group, a C2-40 halogenated alkenyl group, a C2-40 halogenated alkynyl group, a C2-40 halogenated alkenyloxy group, a C2-40 halogenated epoxy group, a C6-40 halogenated aryl group, a C8-40 halogenated aralkenyl group, and a C7-40 halogenated aromatic ring group.

[0102] In the general formula (3), the general formula (2-1), and the general formula (2-2), R1 and R2 are each preferably any one selected from the group consisting of a hydrogen atom, a C1-40 alkyl group, a C1-40 alkoxy group, a C2-40 epoxy group, a C1-40 haloalkyl group, and a C1-40 haloalkoxy group. More preferably, R1 and R2 are each any one selected from the group consisting of a hydrogen atom, a C1-8 alkyl group, a C1-8 alkoxy group, a C2-8 epoxy group, a C1-8 haloalkyl group, and a C1-8 haloalkoxy group.

[0103] In some more preferred embodiments, Y1 represents a divalent organic group represented by the following general formula (2-3):

[0104]

[0105] In some specific embodiments, from the viewpoint of more advantageously achieving the technical effects of the present application, in the photosensitive resin, the content of the diamine-derived structural unit represented by general formula (2) relative to 100 mol % of all diamine-derived structural units is preferably 10 mol % or more, more preferably 15 mol % or more, and even more preferably 20 mol % or more.

[0106] In addition, in the present application, the photosensitive resin further includes a diamine-derived structural unit represented by the following general formula (4):

[0107]

[0108] In the general formula (4), Y2 represents a divalent organic group having a group derived from a quinonediazide compound and 1 to 4 aromatic rings.

[0109] When the photosensitive resin of the present application includes a diamine-derived structural unit represented by general formula (4), the diamine-derived structural unit represented by general formula (4) imparts hydrophobicity to the photosensitive resin before exposure. Furthermore, after exposure, the diamine-derived structural unit undergoes chemical decomposition to become a solubility enhancer, increasing the reaction rate and solubility, thereby significantly improving the photosensitivity and solubility (indicating water solubility) of the photosensitive resin after exposure. In this case, a photosensitive resin composition employing the same, even if containing a small amount (or even no) of photosensitizer, can produce a cured product having excellent photosensitivity, improved solubility after exposure, high resolution, and high hydrophobicity, thereby reducing chemical damage to the substrate.

[0110] In some specific embodiments, from the perspective of more advantageously achieving the technical effect of the diamine-derived structural unit represented by general formula (4) of the present application and improving the mechanical properties of the photosensitive resin, the diamine-derived structural unit represented by general formula (4) is preferably present in the form of a structural unit represented by the following general formula (B), that is, the photosensitive resin of the present application preferably contains the structural unit represented by the following general formula (B) at least in the main chain:

[0111]

[0112] In the general formula (B), X is the same as in the general formula (1), and Y2 is the same as in the general formula (4).

[0113] In some preferred embodiments, from the viewpoint of particularly advantageously achieving the technical effect of the present application comprising a diamine-derived structural unit represented by general formula (4) and more easily obtaining a resin, the quinonediazide compound is preferably a compound having a structure represented by the following general formula (5):

[0114]

[0115] In the general formula (5), R3 is selected from any one of a chlorine atom, a hydroxyl group, a C1-40 alkyl group, a C2-40 alkenyl group, a C1-40 alkoxy group, a C2-40 alkenyloxy group, a C2-40 epoxy group, a C6-40 aryl group, a C8-40 aralkenyl group, a C8-40 aralkynyl group, a C7-40 aromatic ring group, a C1-40 halogenated alkyl group, a C1-40 halogenated alkoxy group, a C2-40 halogenated alkenyl group, a C2-40 halogenated alkynyl group, a C2-40 halogenated alkenyloxy group, a C2-40 halogenated epoxy group, a C6-40 halogenated aryl group, a C8-40 halogenated aralkenyl group, and a C7-40 halogenated aromatic ring group. R3 is preferably selected from any one of a chlorine atom, a hydroxyl group, a C1-40 alkoxy group, a C2-40 epoxy group, a C7-40 aromatic ring group, a C1-40 halogenated alkoxy group, a C2-40 halogenated epoxy group, and a C7-40 halogenated aromatic ring group. R3 is more preferably selected from any one of a chlorine atom, a hydroxyl group, a C1-15 alkoxy group, a C2-15 epoxy group, a C7-15 aromatic ring group, a C1-15 halogenated alkoxy group, a C2-15 halogenated epoxy group, and a C7-15 halogenated aromatic ring group.

[0116] In the present application, in some more specific embodiments, the structural unit derived from diamine represented by the above general formula (4) is more preferably derived from the following diamine: a diamine obtained by reacting a quinonediazide compound in which R3 is a chlorine atom with a diamine containing a phenolic hydroxyl group and 1 to 4 aromatic rings.

[0117] There is no particular limitation on the specific type of the diamine containing a phenolic hydroxyl group and 1 to 4 aromatic rings. Specific examples include, but are not limited to, 4,4′-methylenebis(2-amino-3,6-dimethylphenol), 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl)ether, 3,3′-diamino-4,4′-biphenol, and 9,9-bis(3-amino-4-hydroxyphenyl)fluorene. These diamines may be used alone or in combination of two or more.

[0118] In the present application, in some more specific embodiments, the structural unit derived from diamine represented by the above general formula (4) is particularly preferably derived from a diamine represented by the following general formula (C):

[0119]

[0120] In some preferred embodiments, from the viewpoint of further advantageously achieving the technical effect of the diamine-derived structural unit represented by the general formula (4) of the present application, in the photosensitive resin, the molar ratio of the diamine-derived structural unit represented by the general formula (2) to the diamine-derived structural unit represented by the general formula (4) (diamine-derived structural unit represented by the general formula (2) : diamine-derived structural unit represented by the general formula (4)) is preferably 2:8 to 9:1, more preferably 3:7 to 8:2, and even more preferably 4:6 to 7:3.

[0121] In some preferred embodiments, from the viewpoint of further advantageously achieving the technical effect of the diamine-derived structural unit represented by general formula (4) of the present application, in the photosensitive resin, the content of the diamine-derived structural unit represented by general formula (4) relative to 100 mol % of all diamine-derived structural units is preferably 5 to 30 mol %, more preferably 10 to 25 mol %, and even more preferably 20 to 25 mol %.

[0122] Furthermore, in some specific embodiments, in addition to the diamine-derived structural unit represented by the general formula (2) and the diamine-derived structural unit represented by the general formula (4), the photosensitive resin may further include other diamine-derived structural units.

[0123] There is no particular limitation on the specific types of these other diamines, and specific examples thereof include, but are not limited to, diamines containing hydroxyl groups such as 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl)ether, 3,3'-diamino-4,4'-biphenol, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, and diamines containing hydroxyl groups such as 3-sulfonic acid-4,4'-diaminodiphenyl ether. Sulfonic acid diamines; diamines containing thiol groups such as dithiophenylene diamine; 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3, 3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, and compounds obtained by replacing a portion of the hydrogen atoms of these aromatic rings with alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups, halogen atoms, etc.; such as 2,4-diamino-1,3,5-triazine (guanamine), 2,4-diamino-6-methyl-1,3,5-triazine (methylguanamine), 2,4 These include nitrogen-containing heteroaromatic diamines such as 6-diamino-1,3,5-triazine (benzoguanamine); organosilicon diamines such as 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(p-aminophenyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(p-aminophenethyl)-1,1,3,3-tetramethyldisiloxane, and 1,7-bis(p-aminophenyl)-1,1,3,3,5,5,7,7-octamethyltetrasiloxane; alicyclic diamines such as cyclohexanediamine and diaminodicyclohexylmethane; and diamines containing polyethylene oxide groups. These diamines can be used alone or in combination of two or more.

[0124] (Other structural units)

[0125] Without prejudice to the technical effects of the present application, in addition to the above-mentioned structural units derived from tetracarboxylic dianhydride and the above-mentioned structural units derived from diamine, the photosensitive resin of the present application also includes other structural units, for example, polybenzoxazole structural units, polyamideimide structural units, their precursor structural units, etc.

[0126] In some specific embodiments, the total content of the structural units derived from tetracarboxylic dianhydride and the structural units derived from diamine is preferably 80 mol% or more, more preferably 90 mol% or more, and further preferably 95 mol% or more, relative to 100 mol% of all structural units forming the photosensitive resin.

[0127] In some particularly preferred embodiments, the photosensitive resin of the present application consists only of the structural units derived from tetracarboxylic dianhydride and the structural units derived from diamine, that is, the photosensitive resin of the present application is a photosensitive polyimide resin.

[0128] (Method for producing photosensitive resin)

[0129] In the present application, there is no particular limitation on the method for producing the photosensitive resin, and the photosensitive resin can be formed by methods known in the art.

[0130] In some particularly preferred embodiments, when the photosensitive resin of the present application is composed solely of the aforementioned structural units derived from tetracarboxylic dianhydride and the aforementioned structural units derived from diamine, the photosensitive resin can be formed by a method for producing polyimides known in the art. Examples of the production method include, but are not limited to, a method (1) in which a diamine monomer and a tetracarboxylic dianhydride monomer are preliminarily formed into a polyamic acid, which is then further formed into a photosensitive resin as a polyimide resin, and a method (2) in which a diamine monomer and a tetracarboxylic dianhydride monomer are directly polymerized to form a photosensitive resin as a polyimide resin. Among these, method (2) is more preferred.

[0131] Furthermore, method (2) is preferably carried out as follows: under the protection of an inert gas, dissolving the diamine monomer in a polar solvent, adding a tetracarboxylic dianhydride monomer to the diamine solution, and reacting; after the reaction is completed, isolating the obtained product according to conventional methods in the art. In some specific embodiments, in method (2), the reaction temperature is preferably 150 to 350°C, more preferably 160 to 250°C, and further preferably 180 to 220°C; the reaction time is preferably 1 to 6 hours, more preferably 2.5 to 5 hours. In some specific embodiments, there is no particular limitation on the manner in which the diamine monomer and the tetracarboxylic dianhydride monomer are added, for example, each can be added at once or in batches. Examples of inert gases include, but are not limited to, nitrogen and argon.

[0132] In some specific embodiments, the molar ratio of diamine monomer to tetracarboxylic dianhydride monomer (diamine monomer:tetracarboxylic dianhydride monomer) is preferably 1.1:1 to 1:1.1, more preferably 1.05:1 to 1:1.05, and further preferably 1:1 to 1:1.02.

[0133] In some particularly specific embodiments, the photosensitive resin is formed by: dissolving a diamine monomer in a polar solvent under the protection of an inert gas to obtain a diamine monomer solution, and then adding a diamine monomer containing a structural unit derived from an azobenzene compound (optionally, a diamine monomer containing a structural unit derived from a quinonediazide compound) to the diamine monomer solution to obtain a mixed diamine monomer solution; adding a tetracarboxylic dianhydride monomer to the diamine mixed solution in multiple times and reacting at 200°C for 4 hours; after the reaction is completed, cooling the solution to room temperature and placing it in water to obtain a white precipitate; washing and drying the white precipitate to obtain the target resin.

[0134] <Second Aspect>

[0135] The present application provides a photosensitive resin composition, which includes the photosensitive resin of the present application, a solvent, and an optional photosensitizer.

[0136] The photosensitive resin composition of the present application has a low curing temperature and no significant volume shrinkage during curing, and can produce a cured product with excellent photosensitivity, improved solubility after exposure, and high resolution. Furthermore, the cured product is given hydrophobicity and even reduced chemical damage to the substrate.

[0137] In some specific embodiments, the content of the photosensitive resin is preferably 10-40% by mass, more preferably 15-35% by mass, and even more preferably 20-30% by mass relative to the total amount of the photosensitive resin composition (100% by mass). The photosensitive resin of the present application has been described above in the first aspect and will not be repeated here.

[0138] Therefore, the components of the photosensitive resin composition of the present application other than the photosensitive resin of the present application will be described in detail below.

[0139] (Photosensitive agent)

[0140] In the present application, there is no particular restriction on the specific type of photosensitizer, and it can be appropriately selected as needed. The photosensitizer of the present application is a compound that produces acid by light irradiation (exposure) of ultraviolet light, visible light, etc. The example of the photosensitizer of the present application includes but is not limited to: quinone diazide compounds, diaryl sulfonium salts, triaryl sulfonium salts, dialkyl phenacyl sulfonium salts, diaryl iodonium salts, aryl double salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, aromatic N-oxy imide sulfonic acid esters, aromatic sulfonamides, benzoquinone overlapping sulfonic acid esters, etc. These photosensitizers can be used alone or in combination of two or more.

[0141] In some preferred embodiments, the photosensitizer of the present application is preferably a quinonediazide compound, more preferably a quinonediazide compound having the structure shown in the above general formula (5), and further preferably naphthoquinonediazide-5-sulfonic acid and naphthoquinonediazide-4-sulfonic acid.

[0142] In some specific embodiments, the content of the photosensitizer is preferably 0-40 mass %, more preferably 15-35 mass %, and further preferably 20-30 mass %, relative to the total mass (100 mass %) of the photosensitive resin composition.

[0143] In some more specific embodiments, when the photosensitive resin of the present application includes a diamine-derived structural unit represented by general formula (4), the content of the photosensitizer is preferably 30% by mass or less, more preferably 10% by mass or less, and further preferably 0% by mass (i.e., the photosensitive resin composition does not include a photosensitizer). In some other more specific embodiments, when the photosensitive resin of the present application does not include a diamine-derived structural unit represented by general formula (4), the content of the photosensitizer is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and further preferably 20 to 30% by mass, relative to the total mass (100% by mass) of the photosensitive resin composition.

[0144] (Solvent)

[0145] In the present application, the specific type of the solvent is not particularly limited as long as it can dissolve the components constituting the photosensitive resin composition, and can be appropriately selected according to the coating film thickness, viscosity, and the like. Examples of the solvents of the present application include, but are not limited to: pyrrolidones such as N-methyl-2-pyrrolidone; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; sulfones such as dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, and cyclopentanone; esters such as γ-butyrolactone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, and methyl lactate; alcohols such as diacetone alcohol and 3-methyl-3-methoxybutanol; and aromatic hydrocarbons such as toluene and xylene. These solvents can be used alone or in combination of two or more.

[0146] In some preferred embodiments, ethyl lactate, cyclohexanone, dimethyl sulfoxide, propylene glycol monomethyl ether acetate, γ-butyrolactone and mixtures thereof are preferred, and γ-butyrolactone is more preferred.

[0147] In some specific embodiments, the content of the solvent is preferably 30-80 mass %, more preferably 40-70 mass %, and further preferably 50-60 mass %, relative to the total mass (100 mass %) of the photosensitive resin composition.

[0148] (cross-linking agent)

[0149] In the present application, there is no particular limitation on the specific type of cross-linking agent, and it can be appropriately selected as needed. Examples of the cross-linking agent of the present application include, but are not limited to, benzoxazole, ethylene glycol acrylate, 1,4-cyclohexanediol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-di(p-hydroxyphenyl)propane di(meth)acrylate, tri(meth)acrylate glycerol, trimethylolpropane tri(meth)acrylate, polyoxypropyl trimethylolpropane tri(meth)acrylate, polyoxyethyl trimethylolpropane tri(meth)acrylate, and polyoxyethyl trimethylolpropane tri(meth)acrylate. acrylate, dipentaerythritol penta(meth)acrylate, trimethylolpropane triglycidyl ether (meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, β-hydroxypropyl-β'-(acryloyloxy)-propyl phthalate, phenoxy polyethylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri / tetra(meth)acrylate, etc. These crosslinking agents can be used alone or in combination of two or more.

[0150] In some preferred embodiments, pentaerythritol tri / tetra(meth)acrylate is preferred from the viewpoint of further improving the warpage resistance after curing.

[0151] In some specific embodiments, the content of the crosslinking agent is preferably 1 to 15 mass %, more preferably 2 to 10 mass %, and further preferably 3 to 8 mass %, relative to the total mass (100 mass %) of the photosensitive resin composition.

[0152] (Other components)

[0153] Without prejudice to the technical effects of the present application, the photosensitive resin composition of the present application may further include other components as needed, for example, pigments, dyes, surfactants, photopolymerization initiators, adhesion promoters, thickeners, thixotropic agents, anti-precipitation agents, antioxidants, pH regulators, leveling agents, plasticizers, various other resins, etc.

[0154] In some particularly preferred embodiments, the photosensitive resin composition of the present application does not contain monomers for forming the photosensitive resin of the present application, such as diamine and tetracarboxylic dianhydride, and precursors of the photosensitive resin of the present application, such as polyamic acid, polyamic acid ester, and polyisoimide.

[0155] (Application of the photosensitive resin composition)

[0156] The photosensitive resin composition of the present application is preferably a positive photosensitive resin composition.

[0157] In the present application, there is no particular limitation on the use of the photosensitive resin composition. For example, it can be used to make passivation films, interlayer insulating films, surface protective films, and rewiring insulating films for semiconductor elements, display devices, and light-emitting devices, and is preferably suitable for passivation films.

[0158] <Third Aspect>

[0159] The present application provides a cured product, which is formed by curing the photosensitive resin composition of the present application.

[0160] The cured product of the present application has excellent photosensitivity, exhibits improved solubility after exposure, has high resolution, is hydrophobic, and has little chemical damage to the substrate.

[0161] In some specific embodiments, curing is preferably performed by heating, and there is no particular limitation on the heating method. For example, heating by air blowing, oven heating, or heating on a hot plate can be used. In some more specific embodiments, the curing temperature can be appropriately selected based on the composition of the composition, but is preferably 60 to 200°C, more preferably 75 to 150°C, and even more preferably 85 to 120°C.

[0162] In some specific embodiments, the curing atmosphere may include air, inert gas (nitrogen, argon), etc. In some specific embodiments, the curing pressure may include atmospheric pressure, reduced pressure, increased pressure, and vacuum.

[0163] In some specific embodiments, the curing time is generally 10 seconds to 60 minutes, preferably 30 seconds to 15 minutes, and more preferably 1 minute to 10 minutes.

[0164] <Fourth Aspect>

[0165] The present application provides a pattern forming method comprising the following steps: (1) applying the photosensitive resin composition of the present application to a substrate and curing the composition to form a cured product; (2) exposing the cured product to light through a mask; and (3) developing the cured product using a developer. The pattern forming method of the present application enables efficient formation of fine, high-resolution patterns.

[0166] Each step of the pattern forming method of the present application will be described in detail below.

[0167] (Step (1) of forming a solidified material)

[0168] In this step, the photosensitive resin composition of the present application is coated on a substrate and cured to form a cured product.

[0169] The details of the photosensitive resin composition of the present application are as described above in <Second Aspect> and will not be repeated here.

[0170] In this step, there is no particular limitation on the type of substrate, and a wide range of substrates can be used, including synthetic resins such as polyethylene terephthalate, polyethylene naphthalate, polyethylene, polycarbonate, cellulose triacetate, cellophane, polyimide, polyamide, polyphenylene sulfide, polyetherimide, polyethersulfone, aromatic polyamide, or polysulfone, semiconductor substrates such as silicon wafers, wiring substrates, glass, metal, ceramics, etc.

[0171] In this step, the surface of the substrate may or may not be pretreated as needed. In some specific embodiments, examples of pretreatment methods that can be performed on the surface of the substrate include, but are not limited to: washing with a neutral liquid (e.g., water, or an organic solvent such as ethanol or toluene), washing with an acidic liquid, washing with an alkaline liquid, corona treatment, electrolytic plating solution treatment, electroless plating solution treatment, etc. These methods can be used alone or in combination of two or more.

[0172] In this step, the photosensitive resin composition of the present application can be applied using a coating method known in the art. Examples of coating methods include, but are not limited to, dip coating, spin coating, rod coating, blade coating, curtain coating, screen printing, spray coating, slit coating, and the like. These methods can be used alone or in combination of two or more. In some specific embodiments, spin coating is preferred.

[0173] In this step, the details of the curing method and the cured product are as described above in the <Third Aspect> and will not be repeated here.

[0174] In some specific embodiments, the thickness of the formed solidified material layer is preferably 0.5 to 50 μm, more preferably 1 to 30 μm.

[0175] In some particularly specific embodiments, this step is performed by spin-coating the photosensitive resin composition on a silicon wafer (1200 rpm, 30 seconds), and heating the photosensitive resin composition coated on the silicon wafer on a heating plate at 100° C. for 5 minutes, thereby forming a uniform film layer with a thickness of 10 μm on the silicon wafer.

[0176] (Exposure step (2) of cured product)

[0177] In this step, the formed cured product is exposed through a mask.

[0178] In this step, there are no particular limitations on the exposure light, as long as it can activate the photosensitive resin of the present application. Examples of exposure light include, but are not limited to, visible light, ultraviolet light, X-rays, electron beams, ion beams, and the like. In some preferred embodiments, the exposure light is preferably ultraviolet light or visible light, more preferably ultraviolet light.

[0179] In some specific embodiments, the exposure device can use various devices known in the art, such as a contact aligner, a mirror projection, a stepper exposure machine, and a laser direct exposure device.

[0180] In some specific embodiments, the exposure dose is preferably 500 mJ / cm 2 Below, more preferably 300mJ / cm 2 This is because the cured product formed from the photosensitive composition of the present application has excellent photosensitivity.

[0181] (Development step (3))

[0182] In this step, development is performed using a developer.

[0183] In this step, there is no particular limitation on the developing method, and any photoresist developing method known in the art can be used. Examples of developing methods include, but are not limited to, dip coating (optionally, under ultrasonic irradiation), spin coating, and spray coating. These methods can be used alone or in combination of two or more.

[0184] In some specific embodiments, the developer is preferably an alkaline aqueous solution. In some more specific embodiments, examples of the alkaline substance contained in the alkaline aqueous solution include, but are not limited to: inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia; organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine; and quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide.

[0185] In addition, in some specific embodiments, the developer may further contain a water-soluble organic solvent such as methanol, ethanol, isopropanol, a surfactant, a viscosity reducer, etc. in any content as needed.

[0186] (Other steps)

[0187] In the present application, the pattern forming method of the present application may further include other steps as needed. Examples of other steps include, but are not limited to, a rinsing step, a drying step, and the like.

[0188] In some specific embodiments, the cleaning step can be performed by cleaning the developed solidified material with a cleaning solution. Examples of the cleaning solution include, but are not limited to, water (eg, deionized water), methanol, ethanol, isopropyl alcohol, and the like.

[0189] In some specific embodiments, the drying step may be performed by drying the developed solidified material using a drying method known in the art.

[0190] <Fifth Aspect>

[0191] The present application provides an integrated circuit device (sometimes referred to as a chip) configured with a layer of the cured material of the present application.

[0192] In this application, there is no particular limitation on the specific type of integrated circuit device. In some preferred embodiments, the integrated circuit device of this application can be applied to various terminals such as tablet computers, laptop computers, digital cameras, mobile phones, wearable electronic devices, and virtual reality devices.

[0193] In some specific embodiments, in integrated circuit devices, the layers of the cured product of the present application are suitable for use as protective layers and insulating layers for various components, for example, surface protective films for semiconductor components, stress buffer layers for semiconductor components, insulating films for redistribution layers, protective films for flip-chip devices, protective films for devices with bump structures, interlayer insulating films for multi-layer circuits, insulating materials for passive components, solder resists, covering films, etc.

[0194] In some preferred embodiments, the cured material layer of the present application is preferably suitable for use as a stress buffer coating and an insulating film of a redistribution layer (RDL) of a semiconductor device. The cured material layer of the present application can be used as at least one of a stress buffer coating and an insulating film of a redistribution layer (RDL) of a semiconductor device in the same device.

[0195] For example, during the assembly of integrated circuit (IC) devices, a passivation stress buffering (PSB) process is employed. The photosensitive resin composition of the present invention is cured to form a cured product that forms a stress buffer coating on semiconductor components, thereby alleviating internal stress and preventing degradation of device parameters and package cracking. Specifically, during the IC manufacturing process, after numerous functional transistors and interconnect structures are obtained, the photosensitive resin composition of the present invention is coated thereon to form a stress buffer layer, followed by dicing and subsequent packaging.

[0196] Furthermore, when using redistribution layer (RDL) technology to package integrated circuit (IC) devices, the cured product formed by curing the photosensitive resin composition of the present invention forms an insulating film, ensuring good connections between different components. For example, the originally designed IC circuit contact locations (I / O pads) can be replaced by coating the IC with an insulating layer formed by the photosensitive resin composition of the present invention. A new conductor pattern is then defined through exposure and development. Electroplating is then used to create new metal traces connecting the original aluminum pads to the new bumps or gold pads, achieving circuit redistribution and adapting the IC to different packaging formats.

[0197] In this application, there is no particular limitation on the form of the cured material layer in the integrated circuit device, and the form can be adjusted arbitrarily according to the intended use of the cured material layer. In some specific embodiments, the cured material layer can be a complete cured material layer; in other specific embodiments, the cured material layer can be a cured resin pattern having a specific pattern.

[0198] When the layer of the cured product is a cured resin pattern, the cured resin pattern is preferably formed by the pattern forming method of the present application.

[0199] <Example>

[0200] The following describes the embodiments of the present application in detail, but the present application is not limited to the following embodiments.

[0201] Example 1:

[0202] Under inert gas, 0.014 mol of 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl was dissolved in 24 ml of a polar solvent, to which 0.014 mol of p-diaminoazobenzene was added to prepare a mixed diamine solution. 0.028 mol of pyromellitic dianhydride was added to the mixed solution in multiple portions, and the mixture was reacted at 200°C for 4 hours. After the reaction, the solution was cooled to room temperature and placed in water to obtain a white precipitate. The white precipitate was washed and dried to obtain the target resin.

[0203] To the above-synthesized resin, 0.002 mol of ethylene glycol acrylate, 20 ml of γ-butyrolactone, and 0.002 mol of azidonaphthoquinone-5-sulfonic acid were added to obtain a photosensitive resin composition.

[0204] The photosensitive polyimide composition prepared above was spin-coated on a silicon wafer (1200 rpm, 30 seconds), and the photosensitive polyimide composition coated on the wafer was dried on a hot plate at 100° C. for 5 minutes, thereby forming a uniform film layer A with a thickness of 10 μm on the wafer.

[0205] Example 2:

[0206] Under inert gas, 0.014 mol of 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl was dissolved in 24 ml of a polar solvent, to which 0.028 mol of p-diaminoazobenzene was added to prepare a mixed diamine solution. 0.042 mol of pyromellitic dianhydride was added to the mixed solution in multiple portions, and the mixture was reacted at 200°C for 4 hours. After the reaction, the solution was cooled to room temperature and placed in water to obtain a white precipitate. The white precipitate was washed and dried to obtain the target resin.

[0207] To the above-synthesized resin, 0.003 mol of ethylene glycol acrylate, 30 ml of γ-butyrolactone, and 0.003 mol of azidonaphthoquinone-5-sulfonic acid were added to obtain a photosensitive resin composition.

[0208] The photosensitive polyimide composition prepared above was spin-coated on a silicon wafer (1200 rpm, 30 seconds), and the photosensitive polyimide composition coated on the wafer was dried on a hot plate at 100° C. for 5 minutes, thereby forming a uniform film layer B with a thickness of 10 μm on the wafer.

[0209] Example 3:

[0210] Under inert gas, 0.014 mol of 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl was dissolved in 24 ml of a polar solvent, to which 0.042 mol of p-diaminoazobenzene was added to prepare a mixed diamine solution. To this mixed solution, 0.056 mol of pyromellitic dianhydride was added in multiple portions, and the mixture was reacted at 200°C for 4 hours. After the reaction, the solution was cooled to room temperature and placed in water to obtain a white precipitate. The white precipitate was washed and dried to obtain the target resin.

[0211] To the above-synthesized resin, 0.004 mol of ethylene glycol acrylate, 40 ml of γ-butyrolactone, and 0.004 mol of azidonaphthoquinone-5-sulfonic acid were added to obtain a photosensitive resin composition.

[0212] The photosensitive polyimide composition prepared above was spin-coated on a silicon wafer (1200 rpm, 30 seconds), and the photosensitive polyimide composition coated on the wafer was dried on a hot plate at 100° C. for 5 minutes, thereby forming a uniform film layer C with a thickness of 10 μm on the wafer.

[0213] Example 4:

[0214] Under inert gas, 0.014 mol of 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl was dissolved in 24 ml of a polar solvent, to which 0.014 mol of p-diaminoazobenzene was added to prepare a mixed diamine solution. 0.028 mol of pyromellitic dianhydride was added to the mixed solution in multiple portions, and the mixture was reacted at 200°C for 4 hours. After the reaction, the solution was cooled to room temperature and placed in water to obtain a white precipitate. The white precipitate was washed and dried to obtain the target resin.

[0215] 0.002 mol of ethylene glycol acrylate and 20 ml of γ-butyrolactone were added to the above-synthesized resin to obtain a photosensitive resin composition.

[0216] The photosensitive polyimide composition prepared above was spin-coated on a silicon wafer (1200 rpm, 30 seconds), and the photosensitive polyimide composition coated on the wafer was dried on a hot plate at 100° C. for 5 minutes, thereby forming a uniform film layer with a thickness of 10 μm on the wafer.

[0217] Embodiment 5:

[0218] Under inert gas, 0.007 mol of 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl and 0.007 mol of 4,4′-methylenebis(2-amino-3,6-dimethylphenol) were dissolved in a polar solvent (24 ml). 0.007 mol of quinone diazidesulfonyl chloride and 0.028 mol of p-diaminoazobenzene were added to prepare a mixed diamine solution. 0.042 mol of pyromellitic dianhydride was added to the mixed solution in multiple portions, and the mixture was reacted at 200°C for 4 hours. After the reaction, the solution was cooled to room temperature and placed in water to obtain a white precipitate. The white precipitate was washed and dried to obtain the target resin.

[0219] To the above-synthesized resin, 0.003 mol of ethylene glycol acrylate, 30 ml of γ-butyrolactone, and 0.003 mol of azidonaphthoquinone-5-sulfonic acid were added to obtain a photosensitive resin composition.

[0220] The photosensitive polyimide composition prepared above was spin-coated on a silicon wafer (1200 rpm, 30 seconds), and the photosensitive polyimide composition coated on the wafer was dried on a hot plate at 100° C. for 5 minutes, thereby forming a uniform film layer E with a thickness of 10 μm on the wafer.

[0221] Example 6:

[0222] Under inert gas, 0.007 mol of 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl and 0.007 mol of 4,4′-methylenebis(2-amino-3,6-dimethylphenol) were dissolved in a polar solvent (24 ml). 0.007 mol of quinone diazidesulfonyl chloride and 0.028 mol of p-diaminoazobenzene were added to prepare a mixed diamine solution. 0.042 mol of pyromellitic dianhydride was added to the mixed solution in multiple portions, and the mixture was reacted at 200°C for 4 hours. After the reaction, the solution was cooled to room temperature and placed in water to obtain a white precipitate. The white precipitate was washed and dried to obtain the target resin.

[0223] 0.003 mol of ethylene glycol acrylate and 30 ml of γ-butyrolactone were added to the above-synthesized resin to obtain a photosensitive resin composition.

[0224] The photosensitive polyimide composition prepared above was spin-coated on a silicon wafer (1200 rpm, 30 seconds), and the photosensitive polyimide composition coated on the wafer was dried on a hot plate at 100° C. for 5 minutes, thereby forming a uniform film layer F with a thickness of 10 μm on the wafer.

[0225] Comparative Example 1:

[0226] Under inert gas, 0.014 mol of 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl was dissolved in a polar solvent (24 ml) and added in multiple portions. 0.014 mol of pyromellitic dianhydride was added in multiple portions to the mixed solution. The mixture was reacted at 200°C for 4 hours. After the reaction, the solution was cooled to room temperature and placed in water to obtain a white precipitate. The white precipitate was washed and dried to obtain the target resin.

[0227] To the above-synthesized resin, 0.001 mol of ethylene glycol acrylate, 10 ml of γ-butyrolactone, and 0.001 mol of azidonaphthoquinone-5-sulfonic acid were added to obtain a photosensitive resin composition.

[0228] The photosensitive polyimide composition prepared above was spin-coated on a silicon wafer (1200 rpm, 30 seconds), and the photosensitive polyimide composition coated on the wafer was dried on a hot plate at 100° C. for 5 minutes, thereby forming a uniform film layer D with a thickness of 10 μm on the wafer.

[0229] photosensitivity test

[0230] The four photosensitive polyimides A, B, C, and D prepared above were subjected to photosensitivity testing. The specific steps are as follows:

[0231] The mask with the pattern is placed in the i-line stepper exposure machine at a rate of 100 to 1000 mJ / cm 2 The exposure dose is 10mJ / cm 2 The pre-baked silicon wafer with the A, B, C, and D resin films was exposed at a step distance. After exposure, the wafer was developed twice using an ACT-8 developer with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide and a spin-immersion development method. After rinsing with pure water and drying, the minimum exposure dose at which the exposed portion was completely dissolved was determined. The minimum exposure dose was set to 500 mJ / cm 2 The above situation is considered insufficient (B), and the minimum exposure is set to 300mJ / cm 2 Above and less than 500mJ / cm 2 The situation is considered good (A), and the minimum exposure is less than 300mJ / cm 2 The situation is as extremely good (S).

[0232]

[0233] The flow charts and block diagrams in the accompanying drawings show the possible architecture, functions and operations of the devices, systems, methods and computer program products according to multiple embodiments of the present application. In this regard, each box in the flow chart or block diagram can represent a part for a module, program segment or instruction, and the part for the module, program segment or instruction comprises one or more executable instructions for realizing the logical function of the specification. In some alternative implementations, the functions marked in the box can also occur in a sequence different from that marked in the accompanying drawings. For example, two continuous boxes can actually be performed substantially in parallel, and they can sometimes also be performed in the opposite order, depending on the function involved.

[0234] It should also be noted that each box in the block diagram and / or flowchart, and the combination of boxes in the block diagram and / or flowchart, can be implemented by hardware that performs the corresponding function or action (such as a circuit or ASIC (Application Specific Integrated Circuit)), or can be implemented by a combination of hardware and software, such as firmware.

[0235] Although the present invention has been described herein in conjunction with various embodiments, in the process of implementing the claimed invention, those skilled in the art may understand and implement other variations of the disclosed embodiments by reviewing the drawings, the disclosure, and the appended claims. In the claims, the word "comprising" does not exclude other components or steps, and "a" or "an" does not exclude multiple components. A single processor or other unit may implement several functions listed in the claims. The fact that certain measures are recorded in different dependent claims does not mean that these measures cannot be combined to produce good results.

[0236] The embodiments of the present application have been described above. The above description is illustrative and not exhaustive, and is not limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is selected to best explain the principles of the embodiments, their practical applications, or improvements to the technology in the market, or to enable other persons skilled in the art to understand the embodiments disclosed herein.

Claims

1. A photosensitive resin, characterized in that The main chain includes at least a tetracarboxylic dianhydride-derived structural unit represented by the following general formula (1), a diamine-derived structural unit represented by the following general formula (2), and a diamine-derived structural unit represented by the following general formula (4): In the general formula (1), X represents a tetravalent organic group; in the general formula (2), Y1 represents a divalent organic group having one or more azobenzene compounds, In the general formula (4), Y2 represents a divalent organic group having a group derived from a quinonediazide compound and 1 to 4 aromatic rings.

2. The photosensitive resin according to claim 1, wherein X represents a tetravalent organic group having 1 to 4 at least one cyclic structure selected from an aromatic ring, a 4- to 15-membered aliphatic ring, and a 4- to 15-membered heterocyclic ring.

3. The photosensitive resin according to claim 1, wherein At least the main chain includes a structural unit represented by the following general formula (A): In the general formula (A), X is the same as in the general formula (1), and Y1 is the same as in the general formula (2).

4. The photosensitive resin according to any one of claims 1 to 3, wherein: The azobenzene compound is a compound having a structure represented by the following general formula (3): In the general formula (3), R1 and R2 are each selected from any one of a hydrogen atom, a C1-40 alkyl group, a C2-40 alkenyl group, a C1-40 alkoxy group, a C2-40 alkenyloxy group, a C2-40 epoxy group, a C6-40 aryl group, a C8-40 aralkenyl group, a C8-40 aralkynyl group, a C7-40 aromatic ring group, a C1-40 halogenated alkyl group, a C1-40 halogenated alkoxy group, a C2-40 halogenated alkenyl group, a C2-40 halogenated alkynyl group, a C2-40 halogenated alkenyloxy group, a C2-40 halogenated epoxy group, a C6-40 halogenated aryl group, a C8-40 halogenated aralkenyl group, and a C7-40 halogenated aromatic ring group.

5. The photosensitive resin according to claim 4, wherein Y1 represents a divalent organic group represented by the following general formula (2-1): In the general formula (2-1), R1 and R2 are each selected from any one of a hydrogen atom, a C1-40 alkyl group, a C2-40 alkenyl group, a C1-40 alkoxy group, a C2-40 alkenyloxy group, a C2-40 epoxy group, a C6-40 aryl group, a C8-40 aralkenyl group, a C8-40 aralkynyl group, a C7-40 aromatic ring group, a C1-40 halogenated alkyl group, a C1-40 halogenated alkoxy group, a C2-40 halogenated alkenyl group, a C2-40 halogenated alkynyl group, a C2-40 halogenated alkenyloxy group, a C2-40 halogenated epoxy group, a C6-40 halogenated aryl group, a C8-40 halogenated aralkenyl group, and a C7-40 halogenated aromatic ring group.

6. The photosensitive resin according to any one of claims 1 to 3, wherein: In the photosensitive resin, the content of the diamine-derived structural unit represented by the general formula (2) is 10 mol% or more relative to 100 mol% of all diamine-derived structural units.

7. The photosensitive resin according to claim 1, wherein The photosensitive resin further includes a structural unit represented by the following general formula (B): In the general formula (B), X is the same as in the general formula (1), and Y2 is the same as in the general formula (4).

8. The photosensitive resin according to claim 1, wherein In the photosensitive resin, the molar ratio of the diamine-derived structural unit represented by the general formula (2) to the diamine-derived structural unit represented by the general formula (4) is 2:8 to 9:

1.

9. The photosensitive resin according to claim 1, wherein The quinone diazide compound is a compound having a structure represented by the following general formula (5): In the general formula (5), R3 is any one selected from a chlorine atom, a hydroxyl group, a C1-40 alkyl group, a C2-40 alkenyl group, a C1-40 alkoxy group, a C2-40 alkenyloxy group, a C2-40 epoxy group, a C6-40 aryl group, a C8-40 aralkenyl group, a C8-40 aralkynyl group, a C7-40 aromatic ring group, a C1-40 halogenated alkyl group, a C1-40 halogenated alkoxy group, a C2-40 halogenated alkenyl group, a C2-40 halogenated alkynyl group, a C2-40 halogenated alkenyloxy group, a C2-40 halogenated epoxy group, a C6-40 halogenated aryl group, a C8-40 halogenated aralkenyl group, and a C7-40 halogenated aromatic ring group.

10. A photosensitive resin composition, characterized in that The invention comprises the photosensitive resin according to any one of claims 1 to 9, a solvent and an optional photosensitizer.

11. The photosensitive resin composition according to claim 10, wherein When the photosensitive resin includes the structural unit derived from diamine represented by the general formula (4), the photosensitive resin composition does not include a photosensitizer.

12. The photosensitive resin composition according to claim 10 or 11, characterized in that The photosensitive resin composition includes a cross-linking agent.

13. A solidified product, characterized in that: The photosensitive resin composition is formed by curing the photosensitive resin composition according to any one of claims 10 to 12.

14. A pattern forming method, characterized in that: The following steps are involved: (1) applying the photosensitive resin composition according to any one of claims 10 to 12 on a substrate and curing the composition to form a cured product; (2) exposing the formed solidified material through a mask; (3) Development is performed using a developer.

15. An integrated circuit device, characterized in that: A layer having the cured product according to claim 13 is provided.

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