Polyimide precursor composition, method for producing the same, and use and method for forming insulating layer using the same

Abstract

To provide a reactive polyimide composition that possesses a developing function and can form a polyimide layer exhibiting improved adhesion to copper.SOLUTION: A composition containing a polyimide precursor and an additive compound is provided, wherein the additive contains a first functional group selected from a trialkoxysilyl group or a nitrogen-containing heterocyclic group, and a second functional group selected from a (meth)acrylate group, a nitrogen-containing heterocyclic group, or an amino group, and the polyimide precursor is one selected from (1) a first polyimide precursor having a structural unit derived from a diamine monomer having a silicon-oxygen-silicon group or an acrylic acid group, (2) a second polyimide precursor having an amino-terminated end substituted with a nitrogen-containing heterocyclic group, and (3) a polyimide precursor modified with a compound having an isocyanate group, or a combination of them, and at least one of the polyimide precursor and the additive compound contains a nitrogen-containing heterocyclic group.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to semiconductor technology, and more particularly to a polyimide precursor composition and a method for producing the same, as well as uses and methods for forming insulating layers using the same. [Background technology]

[0002] With the rapid development of the semiconductor industry, the demand for electronic products is trending towards heterogeneous integration, which can achieve higher performance, lower latency, and more functions by combining multiple chips in one packaging device.

[0003] 3D packaging technology can achieve a higher level of heterogeneous integration. A wiring layer structure (e.g., 6P6M or 8P8M structure) including multiple passivation layers (P) and multiple metal layers (M) can provide a highly efficient interconnection network for 3D packaging technology. However, the adhesion between the passivation layer, photosensitive polyimide, metal layer, and copper in the redistribution layer remains a major challenge in maintaining chip performance and reliability. Summary of the Invention [Problem to be solved by the invention]

[0004] In view of the above-mentioned problems, the present disclosure provides a polyimide precursor composition containing a polyimide precursor and an additive compound. The polyimide precursor composition of the present disclosure has a developing function and can form a polyimide layer with improved adhesion to copper. The present disclosure also provides a method for producing the polyimide precursor composition, and uses and methods for forming an insulating layer using the same.

[0005] In some embodiments, the present disclosure provides a polyimide precursor composition. The polyimide precursor composition includes a polyimide precursor and an additive compound. The additive compound includes a first functional group selected from a trialkoxysilyl group or a nitrogen-containing heterocyclic group, and a second functional group selected from a (meth)acrylate group, a nitrogen-containing heterocyclic group, or an amino group. The polyimide precursor is one or a combination of (1) a first polyimide precursor having structural units derived from a diamine monomer having a silicon-oxygen-silicon group (-Si-O-Si-) or an acrylic acid group, (2) a second polyimide precursor having a terminal amino group substituted with a nitrogen-containing heterocyclic group, or (3) a third polyimide precursor modified with a compound having an isocyanate group (-NCO). At least one of the polyimide precursor and the additive compound includes a nitrogen-containing heterocyclic group.

[0006] In some embodiments, the present disclosure provides a method for preparing a polyimide precursor composition, the method comprising: preparing a polyimide precursor; and mixing an additive compound with the polyimide precursor to form a polyimide precursor composition. The additive compound comprises a first functional group selected from a trialkoxysilyl group or a nitrogen-containing heterocyclic group, and a second functional group selected from a (meth)acrylate group, a nitrogen-containing heterocyclic group, or an amino group. The polyimide precursor is one or a combination of (1) a first polyimide precursor having structural units derived from a diamine monomer having a silicon-oxygen-silicon group or an acrylic acid group; (2) a second polyimide precursor having a terminal amino group substituted with a nitrogen-containing heterocyclic group; or (3) a third polyimide precursor modified with a compound having an isocyanate group (—NCO). At least one of the polyimide precursor and the additive compound comprises a nitrogen-containing heterocyclic group.

[0007] In some embodiments, the present disclosure provides the use of the polyimide precursor composition to form an insulating layer on a substrate.

[0008] In some embodiments, the present disclosure provides a method for forming an insulating layer on a substrate using the polyimide precursor composition, the method comprising the steps of mixing the polyimide precursor composition and a solvent to form a polyimide precursor varnish, applying the polyimide precursor varnish to a substrate to form a polyimide precursor layer, performing an exposure process on the polyimide precursor layer to form a polyimide layer, and performing a post-bake process on the polyimide layer. [Brief explanation of the drawings]

[0009] In order to make the objects, features, and advantages of the present disclosure more clearly understood, specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. [Figure 1] 1 is a flowchart of a method for forming an insulating layer on a substrate using a polyimide precursor composition according to one embodiment of the present disclosure. [Figure 2A] 2A-2C are cross-sectional views of the structure at various stages in the method shown in FIG. [Figure 2B] 2B is a cross-sectional view of the structure at each stage in the method shown in FIG. [Figure 2C] 2C is a cross-sectional view of the structure at each stage in the method shown in FIG. DETAILED DESCRIPTION OF THE INVENTION

[0010] It should be further understood that when the terms "comprise" and / or "comprise" are used herein, it denotes the presence of a stated feature element, integer, step, operation, component, ingredient, and / or group thereof, but does not exclude the presence or addition of one or more other feature elements, integers, steps, operations, components, ingredients, and / or groups thereof. Where the singular form "an" is used herein, it is intended to include the plural form unless the context clearly dictates otherwise.

[0011] In this specification, terms such as "first" and "second" may be used to describe each component, member, region, layer, and / or portion, but it should be understood that these components, members, regions, layers, and / or portions are not limited by these terms. These terms are used merely to distinguish one component, member, region, layer, or portion from another component, member, region, layer, or portion.

[0012] It should be understood that, as used herein, terms such as "about," "approximately," and "approximately" typically mean within 20%, preferably within 10%, more preferably within 5%, or within 3%, or within 2%, or within 1%, or within 0.5% of a given value or range. These given quantities are approximate quantities, meaning that even if they are not specifically stated as "about," "approximately," or "approximately," they may include "about," "approximately," or "approximately." Furthermore, numerical values ​​indicated herein may include the numerical values ​​themselves and within a range of error acceptable to a person of ordinary skill in the art. It should be understood that, as used herein, the expression "a to b" expressing a specific numerical range is defined as "≧a and ≦b."

[0013] Unless otherwise defined, all terms used herein (including technical and scientific terms) shall have the same meaning as commonly understood by those skilled in the art. Unless otherwise defined in this disclosure, these terms, for example, terms defined in commonly used dictionaries, should be interpreted to have a meaning consistent with the relevant technical field and the background or context of this application, and should not be interpreted in an idealized or overly strict manner. Below, descriptions that may unnecessarily cause confusion with known functions and structures of the present disclosure will be omitted.

[0014] In the present disclosure, a "monomer" refers to a compound that can be covalently linked to the same or different compounds to form a polymer. In the present disclosure, the term "(meth)acrylic acid group," "(meth)acrylate group," or "hydroxyalkyl (meth)acrylate" indicates that the methyl group in the group or compound is optional. That is, in the present disclosure, the term "(meth)acrylic acid group" includes an acrylic acid group and a methacrylic acid group, in the present disclosure, the term "(meth)acrylate group" includes an acrylate group and a methacrylate group, and in the present disclosure, the term "hydroxyalkyl (meth)acrylate" includes a hydroxyalkyl acrylate and a hydroxyalkyl methacrylate.

[0015] In this disclosure, "C1-C 20 "Alkyl group" refers to a linear, branched, or cyclic aliphatic hydrocarbon monovalent group having from 1 to 20 carbon atoms in the main carbon chain. C1-C 20 Examples of alkyl groups may include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, decyl, dodecyl, cyclohexyl, cyclooctyl, and cyclododecyl groups. 20 The alkyl group may be substituted or unsubstituted C1-C 20 It may be an alkyl group.

[0016] In this disclosure, "C1-C 10 "Alkylene group" refers to a linear, branched, or cyclic aliphatic hydrocarbon divalent group having from 1 to 10 carbon atoms in the main carbon chain. 10 Non-limiting examples of alkylene groups include, but are not limited to, methylene, ethylene, propylene, isobutylene, sec-butylene, tert-butylene, pentylene, isopentylene, hexylene, cyclohexylene, and cyclooctylene groups. 10 The alkylene group may be a substituted or unsubstituted C-C 10 It may be an alkylene group.

[0017] In this disclosure, "C1-C 10 The term "alkylidyne group" refers to a linear, branched, or cyclic aliphatic hydrocarbon trivalent group having from 1 to 10 carbon atoms in the main carbon chain. 10 Non-limiting examples of alkylidine groups include, but are not limited to, methylidine, ethylidine, propylidine, isobutylidine, sec-butylidine, tert-butylidine, pentylidine, isopentylidyne, hexylidine, cyclohexylidine, and cyclooctylidyne groups. 10 The alkylidyne group is a substituted or unsubstituted C1-C 10 It may be an alkylidyne group.

[0018] In this disclosure, "C2-C 10 The term "alkenylene group" refers to a linear, branched, or cyclic aliphatic hydrocarbon divalent group having from 2 to 10 carbon atoms in the main carbon chain and at least one carbon-carbon double bond. 10 Non-limiting examples of alkenylene include, but are not limited to, vinylene, propenylene, isobutylenylene, cyclohexenylene, and cyclooctene groups. 10 The alkenylene group is a substituted or unsubstituted C-C 10 It may be an alkenylene group.

[0019] In this disclosure, "C2-C 10 An "alkenyl idine group" refers to a linear, branched, or cyclic aliphatic hydrocarbon trivalent group having from 2 to 10 carbon atoms in the main carbon chain and at least one carbon-carbon double bond. 10 Non-limiting examples of alkenylidine groups include, but are not limited to, ethenylidine, propenylidine, isobutenylidine, cyclohexenylidine, and cycloctenylidine groups. 10 The alkenyl idine group is a substituted or unsubstituted C2-C 10 It may be an alkenyl idine group.

[0020] In this disclosure, "C6-C 20 "Arylene group" refers to a divalent group containing a carbocyclic aromatic system having from 6 to 20 carbon atoms. 20 Non-limiting examples of arylene groups include, but are not limited to, phenylene, naphthylene, anthracenylene, and phenanthrylene groups. 20 The arylene group is a substituted or unsubstituted C-C 20 It may be an arylene group.

[0021] In this disclosure, "C6-C 20 "Arylidine group" refers to a trivalent group containing a carbocyclic aromatic system having from 6 to 20 carbon atoms. C6-C 20 Non-limiting examples of arylidine groups include, but are not limited to, phenylidine, naphthyridine, anthracenylidine, and phenanthrenylidine groups. 20 The arylidine group may be a substituted or unsubstituted C6-C 20 It may be an arylidine group.

[0022] In this disclosure, "C1-C 20 A "heteroarylene group" refers to a divalent group containing a carbocyclic aromatic system containing heteroatoms as ring-forming atoms and having 1 to 20 carbon atoms. 20Non-limiting examples of heteroarylene groups include, but are not limited to, pyridylene, diazolylene, triazolylene, pyranylene, thienylene, diazinylene, fullerylene, pyrrolylene, imidazolylene, and pyrazolylene groups. 20 Heteroarylene groups are substituted or unsubstituted C-C 20 It may be a heteroarylene group.

[0023] In this disclosure, "C1-C 20 A "heteroarylidine group" refers to a trivalent group containing a carbocyclic aromatic system containing heteroatoms as ring-forming atoms and having 1 to 20 carbon atoms. 20 Non-limiting examples of heteroarylidine groups include, but are not limited to, pyridinylidine, diazolidine, triazolidine, pyranilidine, diazinylidin, thienylidine, furanilidine, pyrrolidine, imidazolidin, and pyrazolidine groups. 20 Heteroarylidine groups are substituted or unsubstituted C1-C 20 It may be a heteroarylidine group.

[0024] The "nitrogen-containing heterocyclic group" of the present disclosure may include a nitrogen-containing heteroaryl group or a nitrogen-containing aliphatic heterocyclic group. In some embodiments, the nitrogen-containing heterocyclic group of the present disclosure may further contain other heteroatoms selected from O, P, S, or a combination thereof. In some embodiments, examples of the nitrogen-containing heterocyclic group may include, but are not limited to, an aziridinyl group, a piperidinyl group, a pyrazolyl group, a morpholinyl group, a tetrazolyl group, a triazolyl group, an imidazolyl group, a benzotriazolyl group, or a benzimidazolyl group. The nitrogen-containing heterocyclic group of the present disclosure may be a substituted or unsubstituted nitrogen-containing heterocyclic group.

[0025] The substituted C1-C 20 Alkyl groups, substituted C1-C 10 Alkylene groups, substituted C2-C 10 Alkenylene group, substituted C2-C 10 Alkenyl groups, substituted C1-C 20 Heteroarylene groups, substituted C6-C 20 Arylene groups, substituted C1-C 10 Alkylidyne groups, substituted C2-C 10 Alkenylidine group, substituted C6-C 20 Arylidine group, substituted C1-C 20 Heteroarylenylidyne groups and substituted nitrogen-containing heterocyclic groups are C1-C12 heterocyclic groups in which at least one hydrogen atom has been replaced by a substituent. 20 Alkyl groups, C1-C 10 Alkylene group, C2-C 10 Alkenylene group, C2-C 10 Alkenyl groups, C1-C 20 Heteroarylene groups, C6-C 20 Arylene groups, C1-C 10 Alkylidyne group, C2-C 10 Alkenyl idine group, C6-C 20 Arylidine group, C1-C 20 Heteroarylidine groups and nitrogen-containing heterocyclic groups. Examples of substituents include, but are not limited to, deuterium, -F, -Cl, -Br, -I, C-C 20 Alkyl groups, and C2-C 10 Alkenyl groups may be included. 10 The alkenyl group is a substituted or unsubstituted C-C 10 It may be an alkenyl group.

[0026] One aspect of the present disclosure provides a polyimide precursor composition comprising a polyimide precursor and an additive compound. The additive compound comprises a first functional group selected from a trialkoxysilyl group or a nitrogen-containing heterocyclic group, and a second functional group selected from a (meth)acrylate group, a nitrogen-containing heterocyclic group, or an amino group. The polyimide precursor is one selected from the following or a combination thereof: (1) a first polyimide precursor having structural units derived from a diamine monomer having a silicon-oxygen-silicon group or an acrylic acid group; (2) a second polyimide precursor having a terminal amino group substituted with a nitrogen-containing heterocyclic group; or (3) a third polyimide precursor modified with a compound having an isocyanate group. At least one of the polyimide precursor and the additive compound comprises a nitrogen-containing heterocyclic group. That is, the polyimide precursor composition of the present disclosure may comprise a first polyimide precursor, a second polyimide precursor, or a third polyimide precursor, and may further comprise an additive compound. At least one of the first polyimide precursor, second polyimide precursor, third polyimide precursor, and additive compound of the present disclosure includes a nitrogen-containing heterocyclic group. By including a nitrogen-containing heterocyclic group in at least one of the first polyimide precursor, second polyimide precursor, third polyimide precursor, and additive compound, the polyimide precursor composition of the present disclosure can have a developing function. In some embodiments, the nitrogen-containing heterocyclic group can be a tetrazolyl group, a triazolyl group, an imidazolyl group, a benzotriazolyl group, or a benzimidazolyl group, although the present disclosure is not limited thereto.

[0027] The first polyimide precursor, the second polyimide precursor, the third polyimide precursor, and the additive compound are described in more detail below. <First polyimide precursor>

[0028] In some embodiments, the first polyimide precursor of the present disclosure may be a polyimide precursor formed by polymerizing a first diamine monomer and a first diacid anhydride monomer.

[0029] The first diamine monomer may be a diamine monomer having a silicon-oxygen-silicon group or an acrylic acid group. In some embodiments, the first diamine monomer may have the structure:

[0030] [ka]

[0031] In the formula, Q 1 has a structure shown in the following formula (1) or formula (2).

[0032] [ka]

[0033] In formula (1), R 1 From R 2 are each independently H or C1-C 20 alkyl groups, and L 1 are C1-C independently 10 Alkylene group or C2-C 10 In formula (1), a may be selected from alkenylene groups, a may be selected from integers of 1 to 10, and * represents the position at which it is bonded to another group. 1 and R 2 may be the same or different, and multiple L in formula (1) 1 may be the same or different from each other. In some embodiments, a in formula (1) is 1 and R 1 and R 2 are both methyl groups, and L 1 are both propylene groups, but the present disclosure is not limited thereto. 3 are C1-C independently 20 alkyl groups, and L 2 are C1-C independently 10 Alkylene group, C2-C 10 alkenylene groups, [ka] ,or [ka] may be selected from the group consisting of R 4 and R 5 are C1-C independently 20 alkyl groups, each A independently being C-C 10 Alkylidyne group, C2-C 10 Alkenyl idine group, C1-C 20 Heteroarylidine group, C6-C 20 In some embodiments, A in formula (2) is a phenylidine group, and R 3 is a methyl group, and L 2 teeth [ka] In some embodiments, the first diamine monomer may be selected from 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate.

[0034] The first dianhydride monomer can be any dianhydride compound that can be polymerized with the first diamine monomer to form a polyimide precursor. In some embodiments, the first dianhydride monomer can have the structure:

[0035] [ka]

[0036] wherein G is one or more C6-C 20 In some embodiments, G is an aryl group. [ka] or [ka] In some embodiments, the first dianhydride monomer may be selected from pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), and combinations thereof.

[0037] In some embodiments, the first polyimide precursor may be formed by polymerizing a first diamine monomer and a first diacid anhydride monomer, and may be a modified polyimide precursor modified with a hydroxyalkyl (meth)acrylate. The hydroxyalkyl (meth)acrylate may have the following structure:

[0038] 4 Z-OH

[0039] wherein Z is a (meth)acrylic acid alkyl group. In some embodiments, examples of hydroxyalkyl (meth)acrylates can include, but are not limited to, hydroxyethyl methacrylate (HEMA).

[0040] By using a diamine monomer having a silicon-oxygen-silicon group or an acrylic acid group as the first diamine monomer, the first polyimide precursor of the present disclosure can have structural units derived from the first diamine monomer. That is, the structural units of the first polyimide precursor can have structural units derived from a diamine monomer having a silicon-oxygen-silicon group or an acrylic acid group. In some embodiments, the first polyimide precursor has structural units derived from a first diamine monomer, such as (1,3-bis(3-aminopropyl)tetramethyldisiloxane) (APDS) or (2-(methacryloyloxy)ethyl 3,5-diaminobenzoate) (ES-HEMA). In some embodiments, the first polyimide precursor can have a structure represented by the following chemical formula:

[0041] [ka]

[0042] In the formula, R is a carboxylic acid group (-COOH) or -COOZ, where Z is the same as Z in the above hydroxyalkyl (meth)acrylate. 1 is Q in the first diamine monomer 1 G is the same as G in the first diacid anhydride monomer. n may be an integer of 30 to 130. In some embodiments, the weight average molecular weight (Mw) of the first polyimide precursor may be 20,000 to 50,000 g / mol. <Second polyimide precursor>

[0043] The second polyimide precursor of the present disclosure may be a polyimide precursor formed by polymerizing a second diamine monomer, a second diacid anhydride monomer, and an amino compound having a nitrogen-containing heterocyclic group.

[0044] The second diamine monomer may have the structure:

[0045] [ka]

[0046] In the formula, Q 2 may have a structure shown in formula (1), formula (2) or formula (3) below.

[0047] [ka]

[0048] In formula (3), B is independently C1-C 10 Alkylene group, C2-C 10 Alkenylene group, C1-C 20 Heteroarylene groups, C6-C 20 arylene groups, or combinations thereof; L 3 are each independently a single bond, an oxygen linking group (-O-), or C1-C 10 Alkylene group, or C2-C 10 The B's in formula (3) may be the same or different from one another and may be substituted or unsubstituted, for example, substituted with an alkyl group or a fluoroalkyl group. When b is greater than 1, the plurality of L's in formula (3) may be substituted with an alkyl group or a fluoroalkyl group. 3 In some embodiments, b in formula (3) is 1, each B is a phenylene group, a toluylene group, or a benzotrifluoride, and L 3is a single bond or an oxygen linking group, although the present disclosure is not limited thereto. Formulas (1) and (2) have been described above and will not be repeated here. In some embodiments, the second diamine monomer may be selected from 1,3-bis(3-aminophenoxy)benzene (APB), 4,4'-diamino-2,2'-dimethylbiphenyl (M-Tolidine, m-TBHG), 2,2'-bis(trifluoromethyl)-(1,1'-diphenyl)-4,4'-diamine (2,2'-bis(trifluoromethyl)benzidine, TFMB), (1,3-bis(3-aminopropyl)tetramethyldisiloxane) (APDS), and (2-(methacryloyloxy)ethyl 3,5-diaminobenzoate) (ES-HEMA).

[0049] The second dianhydride monomer can be any dianhydride compound that can be polymerized with the second diamine monomer to form a polyimide precursor. Similar to the first dianhydride monomer, the second dianhydride monomer can have the structure:

[0050] [ka]

[0051] wherein G is as described above and will not be repeated here. In some embodiments, the second dianhydride monomer may be selected from pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, or a combination thereof.

[0052] The amino compound having a nitrogen-containing heterocyclic group may include an amino compound having a nitrogen-containing heteroaryl group or an amino compound having a nitrogen-containing aliphatic heterocyclic group. In some embodiments, the amino compound having a nitrogen-containing heterocyclic group may be an amino compound containing a tetrazolyl group, a triazolyl group, or an imidazolyl group, but the present disclosure is not limited thereto. In some embodiments, the amino compound having a nitrogen-containing heterocyclic group may have the following structure:

[0053] [ka]

[0054] wherein E is a nitrogen-containing heterocyclic group. In some embodiments, E is a nitrogen-containing heteroaryl group. In some embodiments, E is a tetrazolyl group, a triazolyl group, an imidazolyl group, a benzotriazolyl group, or a benzimidazolyl group, although the present disclosure is not limited thereto. In some embodiments, the amino compound having a nitrogen-containing heterocyclic group may be 5-aminotetrazole (5-ATZ).

[0055] By using an amino compound having a nitrogen-containing heterocyclic group, the second polyimide precursor of the present disclosure can have a terminal amino group substituted with the nitrogen-containing heterocyclic group. In some embodiments, the second polyimide precursor can have a terminal amino group substituted with 5-aminotetrazole. In some embodiments, the second polyimide precursor can have a structure represented by the following chemical formula:

[0056] [ka]

[0057] where R is a carboxylic acid group (-COOH) and Q 2 is Q in the second diamine monomer 2where G is the same as G in the second diacid anhydride monomer, E is the same as E in the amino compound having a nitrogen-containing heterocyclic group, and n may be an integer of 30 to 130. In some embodiments, the weight average molecular weight (Mw) of the second polyimide precursor may be 20,000 to 50,000 g / mol. <Third polyimide precursor>

[0058] The third polyimide precursor of the present disclosure may be a modified polyimide precursor obtained by polymerizing a third diamine monomer, a fourth diamine monomer having a hydroxy group, and a third diacid anhydride monomer, and then modifying the polymerized product with a compound having an isocyanate group (—NCO).

[0059] Similar to the second diamine monomer, the third diamine monomer may have the structure:

[0060] [ka]

[0061] In the formula, Q 3 may have a structure represented by the following formula (1), (2), or (3):

[0062] [ka]

[0063] Formulas (1) to (3) are as described above and will not be repeated here. In some embodiments, the third diamine monomer may be selected from 1,3-bis(3-aminophenoxy)benzene (APB), 4,4'-diamino-2,2'-dimethylbiphenyl (M-Tolidine, m-TBHG), 2,2'-bis(trifluoromethyl)-(1,1'-diphenyl)-4,4'-diamine (2,2'-bis(trifluoromethyl)benzidine, TFMB), 1,3-bis(3-aminopropyl)tetramethyldisiloxane (APDS), and 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (ES-HEMA).

[0064] In some embodiments, the fourth diamine monomer may have the structure:

[0065] [ka]

[0066] In the formula, Y may have a structure represented by the following formula (4):

[0067] [ka]

[0068] In formula (4), C is independently C1-C 10 Alkylidyne group, C2-C 10 Alkenyl idine group, C1-C 20 Heteroarylidine group, C6-C 20 L may be selected from an aryl group, an aryl group, or a combination thereof, and C may be substituted with a hydroxy group. 4 are each independently a single bond, an oxygen linking group (-O-), or C1-C 10 Alkylene group, or C2-C 10alkenylene groups, c may be selected from integers of 1 to 10, and L 4 may be substituted or unsubstituted, for example, may be substituted with an alkyl group. * indicates the position where it is bonded to another group. C in formula (4) may be the same or different from each other. When c is greater than 1, multiple L in formula (4) 4 may be the same or different from each other. In some embodiments, c in formula (4) is 1, C is a phenylidine group or a hydroxyphenylidine group, and L 4 is a methylene group substituted with a dimethyl group, although the disclosure is not limited thereto. In some embodiments, the fourth diamine monomer can be 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP).

[0069] The third dianhydride monomer can be any dianhydride compound that can be polymerized with the third diamine monomer and the fourth diamine monomer to form a polyimide precursor. Similar to the first dianhydride monomer, the third dianhydride monomer can have the structure:

[0070] [ka]

[0071] wherein G is as described above and will not be repeated here. In some embodiments, the third dianhydride monomer may be selected from pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, or a combination thereof.

[0072] The compound having an isocyanate group (-NCO) may have the structure:

[0073] [ka]

[0074] In the formula, each D is independently triC1-C 10 Alkoxysilane, DiC1-C 10 Alkoxysilane or Mono C1-C 10 alkoxysilanes, and L 5 are each independently a single bond, an oxygen linking group (-O-), or C1-C 10 Alkylene group, or C2-C 10 In some embodiments, the compound having an isocyanate group may include 3-(triethoxysilyl)propyl isocyanate, diethoxy(3-isocyanatopropyl)silane, or ethoxy(3-isocyanatopropyl)silane.

[0075] By modifying the polyimide precursor formed by polymerizing the third diamine monomer, the fourth diamine monomer, and the third diacid anhydride monomer using a compound having an isocyanate group, the third polyimide precursor of the present disclosure can have a structure represented by the following chemical formula:

[0076] [ka]

[0077] where R is a carboxylic acid group (-COOH) and Q 3 is Q in the third diamine monomer 3 and Y is the same as Y in the fourth diamine monomer, G is the same as G in the third dianhydride monomer, and D and L are 5 is the D and L in the compound having an isocyanate group. 5 where n may be an integer of 1 to 100, and m may be an integer of 1 to 100. <Additive compounds>

[0078] The additive compound may include a first functional group selected from a trialkoxysilyl group or a nitrogen-containing heterocyclic group, and a second functional group selected from a (meth)acrylate group, a nitrogen-containing heterocyclic group, or an amino group. In some embodiments, the additive compound may have the structure:

[0079] 19 X 1 -L 6 -X 2

[0080] In the formula, X 1 is a first functional group selected from a trialkoxysilyl group or a nitrogen-containing heterocyclic group, and X 2 is a second functional group selected from a (meth)acrylate group, a nitrogen-containing heterocyclic group, or an amino group, and L 6 may each independently be selected from a single bond or a divalent linking group. In some embodiments, the divalent linking groups are each independently selected from an oxygen linking group (—O—), a C-C 10 Alkylene group, or C2-C 10 In some embodiments, X may be selected from the group consisting of an alkenylene group. 1 and / or X 2 may be a tetrazolyl group, a triazolyl group, an imidazolyl group, a benzotriazolyl group, or a benzimidazolyl group, and L 6 is C1-C 10 In some embodiments, X may be an alkylene group. 1 may be a trialkoxysilyl group, and X 2 may be selected from a (meth)acrylate group, a nitrogen-containing heterocyclic group, or an amino group, and L 6 is C1-C 10In some embodiments, the additive compound may include 3-(methacryloxy)propyltrimethoxysilane (KBM-503), 3-aminopropyltrimethoxysilane (KBM-903), X-12-1214A (purchased from Shin-Etsu Chemical Co., Ltd.), TC-7902-02 (purchased from Kanriyo Enterprise Co., Ltd.), or a combination thereof.

[0081] Through experiments, the inventors have found that certain additive compounds disclosed herein form coordinate bonds with copper and can also form covalent bonds with the first polyimide precursor, the second polyimide precursor, and / or the third polyimide precursor. This improves adhesion between the polyimide layer formed using the polyimide precursor composition disclosed herein and the substrate. Furthermore, the present disclosure also provides a method for suppressing the generation of copper ions during the exposure process by incorporating a nitrogen-containing heterocyclic group (e.g., tetrazolyl, triazolyl, or imidazolyl) in at least one of the polyimide precursor and the additive compound. This prevents the reaction of copper ions with the polyimide precursor to form polyamic acid-copper salts, thereby resolving the problem of polyamic acid-copper salts being poorly soluble in developers and improving the precision of the polyimide layer formed during the development process.

[0082] In some embodiments, the polyimide precursor composition of the present disclosure may further include a cross-linker, which is a compound having a polymerizable group (e.g., an alkenyl group). In some embodiments, the cross-linker may be an acrylate compound. Examples of the acrylate compound may include, but are not limited to, tris(2-acryloyloxyethyl) isocyanurate, glycidyl methacrylate, polyethylene glycol diacrylate, ethoxylated pentaerythritol tetraacrylate, or a combination thereof. The cross-linker can form an insoluble three-dimensional network structure by cross-linking with other components in the formulation (e.g., polyimide precursors in the polyimide precursor composition) during exposure or heat treatment. This cross-linking reaction makes the material in the exposed areas solvent resistant and keeps it insoluble in the developer, thereby allowing the pattern to be developed.

[0083] In some embodiments, the polyimide precursor composition of the present disclosure may further contain other polymers in addition to the polyimide precursor and additive compound described above. For example, the polyimide precursor composition of the present disclosure may further contain, for example, 100 parts by weight or less, or 50 parts by weight or less, of the other polymers, based on 100 parts by weight of the polyimide precursor. The other polymers may be, but are not limited to, polyamic acids, polyimides, or other types of polyimide precursors. By appropriately selecting the other polymers, the processability, physical properties, or compatibility with substrates of the polyimide layer formed using the polyimide precursor of the present disclosure can be further adjusted to meet various application needs.

[0084] In some embodiments, the polyimide precursor composition of the present disclosure may further comprise a photoinitiator, a reaction inhibitor, and / or a leveling agent. The photoinitiator may be a commercially available product capable of absorbing light of a specific wavelength and generating radicals. Examples of photoinitiators include, but are not limited to, BASF's Irgacure® PBG-345, Irgacure® 907, Irgacure® 369, and Irgacure® 819. These photoinitiators absorb ultraviolet light of a specific wavelength during the exposure step and cleave to generate radicals. The generated radicals can cause a crosslinking reaction of a crosslinker having a polymerizable group (e.g., an alkenyl group) in the formulation, forming a three-dimensional network structure in the exposed region of the material, thereby reducing its solubility in the developer.

[0085] The reaction inhibitor may be a commercially available product, and examples include, but are not limited to, Merck's 4-methoxyphenol and / or hydroquinone. The purpose of the reaction inhibitor is to prevent the crosslinking agent containing a polymerizable group (e.g., an alkenyl group) from undergoing crosslinking under unexposed conditions. Because crosslinking agents typically contain polymerizable functional groups, they tend to undergo spontaneous polymerization during storage or preparation, resulting in increased viscosity of the varnish, reduced operability, and deterioration of photoresist performance. Adding a reaction inhibitor can prevent spontaneous polymerization under unexpected conditions, thereby extending the shelf life of the composition and maintaining its stability.

[0086] The leveling agent may be a commercially available product, and examples include, but are not limited to, Fluorosurfactant FC-4430, available from Rokugo Chemicals, and / or LS-430, available from Kusumoto Chemicals. The leveling agent can improve the smoothness and uniformity of the coated film layer surface. In actual manufacturing processes, differences in the surface tension or evaporation rate of each component in the formulation can result in defects such as micro-unevenness, wavy patterns, or shrinkage on the film surface. The addition of a leveling agent can enhance the self-leveling ability of the thin film during coating and drying, effectively reducing flow marks or other surface defects caused by surface tension gradients, thereby improving the conformality and resolution of pattern edges.

[0087] In some embodiments, the polyimide precursor compositions of the present disclosure are free of benzotriazole (BTA).

[0088] In some embodiments, the polyimide precursor composition of the present disclosure may include, per 100 parts by weight of polyimide precursor, 0.001 to 2 parts by weight of the additive compound, e.g., 0.01 to 2 parts by weight, 1 part by weight or less, or 0.5 parts by weight or less of the additive compound. In some embodiments, per 100 parts by weight of polyimide precursor, the polyimide precursor composition of the present disclosure may include 20 parts by weight or less, e.g., 18 parts by weight or less, or 16 parts by weight or less of the crosslinking agent. In some embodiments, per 100 parts by weight of polyimide precursor, the polyimide precursor composition of the present disclosure may include 0.1 to 2 parts by weight of a photoinitiator, 0.1 to 1 part by weight of a reaction inhibitor, and / or 0.1 to 1 part by weight of a leveling agent.

[0089] In some embodiments, the polyimide precursor composition of the present disclosure may further include a solvent to form a polyimide precursor varnish. Examples of solvents include, but are not limited to, N-ethylpyrrolidone (NEP). In some embodiments, the polyimide precursor varnish of the present disclosure may include 60 to 70 wt % of the solvent and 30 to 40 wt % of the polyimide precursor composition of the present disclosure (i.e., polyimide precursor and additive compound, as well as optional photoinitiators, optional reaction inhibitors, optional crosslinkers, optional leveling agents, or combinations thereof), where the total weight of the polyimide precursor varnish is 100 wt %.

[0090] Another aspect of the present disclosure provides a method for preparing a polyimide precursor composition, which includes preparing a polyimide precursor and mixing an additive compound with the polyimide precursor to form a polyimide precursor composition, the polyimide precursor and the additive compound being as described above. That is, the polyimide precursor may be selected from a first polyimide precursor, a second polyimide precursor, and a third polyimide precursor, the additive compound may include a first functional group selected from a trialkoxysilyl group or a nitrogen-containing heterocyclic group and a second functional group selected from a (meth)acrylate group, a nitrogen-containing heterocyclic group, or an amino group, and at least one of the polyimide precursor and the additive compound includes a nitrogen-containing heterocyclic group.

[0091] The methods for producing the first polyimide precursor, the second polyimide precursor, and the third polyimide precursor are as described above. Specifically, the first polyimide precursor may be a polyimide precursor formed by polymerizing a first diamine monomer and a first diacid anhydride monomer, where the first diamine monomer may be a diamine monomer having a silicon-oxygen-silicon group or an acrylic acid group. The second polyimide precursor may be a polyimide precursor formed by polymerizing a second diamine monomer, a second diacid anhydride monomer, and an amino group compound having a nitrogen-containing heterocyclic group. The third polyimide precursor may be a modified polyimide precursor formed by polymerizing a third diamine monomer, a fourth diamine monomer, and a third diacid anhydride monomer, and then modifying the resulting polymer with a compound having an isocyanate group (-NCO), where the fourth diamine monomer has a hydroxy group.

[0092] Another aspect of the present disclosure relates to the use of the polyimide precursor composition for forming an insulating layer on a substrate. Yet another aspect of the present disclosure relates to a method for forming an insulating layer on a substrate using the polyimide precursor composition. FIG. 1 is a flowchart of a method for forming an insulating layer on a substrate using a polyimide precursor composition according to one embodiment of the present disclosure. FIGS. 2A to 2C are cross-sectional views of the structure at each stage in the method shown in FIG. 1. As shown in FIG. 1, the method for forming an insulating layer on a substrate using the polyimide precursor composition includes step S101 of mixing the polyimide precursor composition and a solvent to form a polyimide precursor varnish, step S103 of applying the polyimide precursor varnish on a substrate to form a polyimide precursor layer, step S105 of performing an exposure process on the polyimide precursor layer to form a polyimide layer, and step S107 of performing a post-baking process on the polyimide layer.

[0093] In step S101, a polyimide precursor varnish can be formed by mixing a polyimide precursor composition and a solvent in a weight ratio of about 30-40:60-70. The polyimide precursor composition and the solvent are as described above, and will not be repeated here.

[0094] See FIG. 2A. The substrate 201 in step S103 may include a silicon substrate or a copper-containing substrate. In some embodiments, the copper-containing substrate may include a base and a copper foil or copper metal layer disposed on the base, but the present disclosure is not limited thereto. The polyimide precursor varnish obtained in step S101 may be disposed on the substrate 201 in any manner in step S103 to form a polyimide precursor layer 203.

[0095] See FIG. 2B. The polyimide precursor layer 203 is converted into a polyimide layer 205 by an exposure process in step S105. In step S105, the additive compound in the polyimide precursor varnish forms a coordinate bond with the substrate 201 and a covalent bond with the polyimide precursor in the polyimide precursor varnish, resulting in the formation of a polyimide layer 205 with enhanced adhesion to the substrate 201. Furthermore, in embodiments where the substrate 201 is a copper-containing substrate, at least one of the polyimide precursor and the additive compound in the polyimide precursor varnish contains a nitrogen-containing heterocyclic group (e.g., tetrazolyl, triazolyl, or imidazolyl), which can suppress the generation of copper ions during the exposure process in step S205. This prevents the copper ions from bonding with the polyimide precursor to form a polyamic acid-copper salt, reduces the amount of residual unexposed areas, and improves the accuracy of pattern transfer and the conformality of the pattern of the polyimide layer 205. Finally, see FIG. 2C. When the polyimide layer 205 is subjected to a post-baking process in step S107, an insulating layer 207 is formed.

[0096] In summary, the insulating layer 207 formed on the substrate 201 using the polyimide precursor composition of the present disclosure has higher precision and improved adhesion to the substrate 201.

[0097] Hereinafter, one or more embodiments of the present disclosure will be described in detail with reference to examples, but these examples are only used to explain the embodiments of the present disclosure and are not intended to limit the scope of the embodiments of the present disclosure.

[0098] Synthesis of polyimide precursors 1-4

[0099] Synthesis Example 1

[0100] In a three-necked round-bottom flask equipped with a mechanical stirrer and a thermometer under nitrogen, 34.8 mol of 2,2'-bis(trifluoromethyl)-(1,1'-diphenyl)-4,4'-diamine (TFMB), 40.9 mol of 4,4'-diamino-2,2'-dimethylbiphenyl (m-TBHG), and 3.9 mol of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (APDS) were dissolved in γ-butyrolactone (GBL) to form a solution. Then, 50 mol of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 50 mol of pyromellitic dianhydride (PMDA) were added to the solution to form a mixture.

[0101] The mixture was heated to 50°C and maintained at that temperature for 180 minutes to form a reaction mixture. The reaction mixture was then cooled to 4°C, and trifluoroacetic anhydride diluted with GBL (TFAA in GBL, 42 wt%) was added. After the reaction was continued at 4°C for 180 minutes, 800 mol of hydroxyethyl methacrylate (HEMA) was added and the reaction was continued overnight to form a reaction solution.

[0102] The reaction solution was precipitated with water, and then filtered to collect the solid. The solid was dried under high vacuum. The dried solid was Polyimide Precursor 1.

[0103] Synthesis Example 2

[0104] Under nitrogen, in a three-necked round-bottom flask equipped with a mechanical stirrer and a thermometer, 20 mmol of 1,3-bis(3-aminophenoxy)benzene (APB) was dissolved in dimethylacetamide (DMAc) at 60°C for 10 minutes to form a solution, followed by addition of 50 mmol of pyromellitic dianhydride to the solution to form a mixture, which was then stirred for 20 minutes to obtain a mixed solution.

[0105] 40 mmol of 4,4'-diamino-2,2'-dimethylbiphenyl, 35 mmol of (2-(methacryloyloxy)ethyl 3,5-diaminobenzoate, and 5 mmol of (1,3-bis(3-aminopropyl)tetramethyldisiloxane were added to the above mixed solution, and then stirred for 10 minutes to obtain a reaction solution. Next, 50 mmol of pyromellitic dianhydride was added to the above reaction solution, and then stirred for 10 minutes to obtain a reaction mixture. The reaction mixture was reacted at 60°C for 120 minutes and then cooled to room temperature to obtain polyimide precursor 2 with a final reaction concentration of 33 wt%.

[0106] Synthesis Example 3

[0107] Under nitrogen, in a three-necked round-bottom flask equipped with a mechanical stirrer and a thermometer, 20 mmol of 1,3-bis(3-aminophenoxy)benzene (APB) and 10 mmol of 5-aminotetrazole (5-ATZ) were dissolved in dimethylacetamide (DMAc) at 60°C for 10 minutes to form a solution. Then, 50 mmol of pyromellitic dianhydride was added to the solution to form a mixture, which was then stirred for 20 minutes to obtain a mixed solution.

[0108] 40 mmol of 4,4'-diamino-2,2'-dimethylbiphenyl, 35 mmol of (2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (ES-HEMA), and 5 mmol of (1,3-bis(3-aminopropyl)tetramethyldisiloxane were added to the above mixed solution and stirred for 10 minutes to obtain a reaction solution. Next, 50 mmol of pyromellitic dianhydride was added to the above reaction solution, and then stirred for 10 minutes to obtain a reaction mixture. The above reaction mixture was reacted at 60°C for 120 minutes and then cooled to room temperature to obtain polyimide precursor 3 with a final reaction concentration of 31 wt%.

[0109] Synthesis Example 4

[0110] Under nitrogen, in a three-necked round-bottom flask equipped with a mechanical stirrer and a thermometer, 20 mmol of 1,3-bis(3-aminophenoxy)benzene was dissolved in dimethylacetamide (DMAc) at 60°C for 10 minutes to prepare a solution. Then, 50 mmol of pyromellitic dianhydride was added to the solution to prepare a mixture, which was then stirred for 20 minutes to obtain a mixed solution.

[0111] 40 mmol of 4,4'-diamino-2,2'-dimethylbiphenyl, 35 mmol of (2-(methacryloyloxy)ethyl 3,5-diaminobenzoate) (ES-HEMA), and 5 mmol of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP) were added to the above mixed solution and stirred for 10 minutes to obtain a reaction solution. Next, 50 mmol of pyromellitic dianhydride was added to the above reaction solution and stirred for 10 minutes to obtain a mixture. The above reaction mixture was reacted at 60°C for 120 minutes and then cooled to room temperature to obtain a reaction mixture. Next, 40 mmol of 3-isocyanatopropyltriethoxysilane was added to the above reaction mixture to obtain polyimide precursor 4 with a final reaction concentration of 31.8 wt%.

[0112] Weight average molecular weight analysis

[0113] A dimethylacetamide mixed solvent was prepared by mixing 3760 g of dimethylacetamide, 13.8 g of phosphoric acid (H3PO4), 3.76 g of tetrahydrofuran (THF), and 10.42 g of lithium bromide (LiBr).

[0114] Approximately 0.005 g of each of polyimide precursors 1 to 4 was taken and 1 mL of a dimethylacetamide mixed solvent (containing 0.04% toluene) was added to obtain molecular weight samples 1 to 4. After filtering the molecular weight samples 1 to 4 through a 0.45 μm filter, the weight-average molecular weights of polyimide precursors 1 to 4 were analyzed by gel permeation chromatography (GPC) under the following parameters. The results are shown in Table 1 below. Instrument conditions: K & alpha = 0.00016, 0.7 (samples are treated as polystyrene standards) Mobile phase: DMAc mixed solvent, analysis time: 45min, flow rate: 1.0mL / min column: Shodex KD-803, 5μm*8mm*300mm Shodex KD-804, 7μm*8mm*300mm Shodex KD-805, 10μm*8mm*300mm Injection volume: 50 μL, column temperature: 40°C, RI temperature: 40°C

[0115] [Table 1]

[0116] Preparation of polyimide precursor varnishes 1-13

[0117] Polyimide precursors 1 to 4 were each dissolved in N-ethylpyrrolidone (NEP) and stirred overnight to form a solution. A crosslinker, benzotriazole, reaction inhibitor, leveling agent, additive compound, and photoinitiator were sequentially added to the solution to form a precursor solution. The precursor solution was mixed and degassed using a planetary centrifugal mixer, and then filtered through a capsule filter to obtain polyimide precursor varnishes 1 to 13.

[0118] Among the polyimide precursor varnishes 1-13, various combinations of polyimide precursors 1-4, crosslinking agent, benzotriazole, reaction inhibitor, leveling agent, additive compound, and photoinitiator are defined as polyimide precursor compositions 1-13 of the present disclosure. That is, polyimide precursor varnishes 1-13 each contain polyimide precursor compositions 1-13 and N-ethylpyrrolidone as a solvent. Polyimide precursor varnishes 1-13 each contain 40 wt% of polyimide precursor compositions 1-13 and 60 wt% of N-ethylpyrrolidone, assuming the total weight of the polyimide precursor varnish is 100 wt%. The components used in polyimide precursor compositions 1-13 and the ratios of each component are shown in Tables 2 to 4 below.

[0119] [Table 2]

[0120] [Table 3]

[0121] [Table 4]

[0122] Viscosity Test

[0123] A copper-containing substrate was prepared by cleaning with 5% H2SO4 for 30 seconds and then with H2O for 10 seconds. Polyimide precursor varnishes 1 to 13 were each spin-coated onto the dried copper-containing substrate to form a polyimide precursor varnish layer measuring 50 mm x 50 mm x 0.3 mm. The polyimide precursor varnish layer was soft-baked at 100 to 150°C for 30 to 120 seconds to form a polyimide precursor layer. Next, the polyimide precursor layer was exposed to an exposure dose of 150 to 300 mJ / cm 2The resulting polyimide layer was then exposed to ultraviolet light with a wavelength of 365 nm to form a polyimide layer. The polyimide layer was then heat-cured in a nitrogen reflow oven at 260°C for 1.5 hours at a heating rate of 5°C / min, and then cooled to room temperature at a rate of 5°C / min (the oxygen concentration during curing must be controlled to within 30 ppm), completing the preparation of viscosity samples 1 to 13.

[0124] The adhesive strength of viscosity samples 1 to 13 was measured at a speed of 5 mm / min by a stud pull test according to MIL-STD-883, and the results are shown in Table 5 below.

[0125] [Table 5]

[0126] Development test

[0127] Polyimide precursor varnishes 1 to 13 were each spin-coated onto a 6-inch silicon wafer to form a polyimide precursor varnish layer measuring 50 mm x 50 mm x 0.3 mm. The polyimide precursor varnish layer was soft-baked at 100 to 150°C for 30 to 120 seconds to form a polyimide precursor layer. Next, the polyimide precursor layer was exposed to an exposure dose of 150 to 300 mJ / cm. 2 The silicon wafer with the polyimide layer formed was then immersed in a developer bath (i.e., cyclopentanone), then in a buffer bath (i.e., a 1:1 volume mixture of cyclopentanone and 1-methoxy-2-propanol acetate), and finally in a 1-methoxy-2-propanol acetate bath to obtain developed samples 1-13. After drying with nitrogen, developed samples 1-13 were hard-baked at 100°C for 20 minutes (post-development baking) to obtain lithography samples 1-13.

[0128] The development results of lithography samples 1-13 were confirmed using an optical microscope and a reflectometer. The results are shown in Table 6 below. Lithography samples 1-13 were observed under an optical microscope at 50x or 200x magnification. If the underlying copper layer was clearly visible in the hole opening area, the hole opening was successful and recorded as "pass" (indicated by a circle in Table 6). In contrast, if the copper layer was not visible and there was no clear difference in brightness in the developed area under the microscope, it was considered to have no contrast, indicating that the copper layer was not effectively exposed, and recorded as "fail" (indicated by an "x" in Table 6). The "contrast ratio" here refers to the difference in reflective brightness between the copper layer and the upper polyimide layer under an optical microscope. If the copper layer is not exposed or the remaining film layer is too thick, there is insufficient contrast, making it impossible to determine the hole opening status, which is expressed as "no contrast ratio."

[0129] [Table 6]

[0130] As can be seen from Tables 2 to 5, the adhesive strength of polyimide precursor compositions that do not contain benzotriazole (BTA) is relatively high. As can be seen from Tables 2 to 4 and Table 6, when either the additive compound or the polyimide precursor contains a nitrogen-containing heterocyclic group, the polyimide precursor composition has a developing function. In other words, by substituting an additive compound containing a nitrogen-containing heterocyclic group for benzotriazole (BTA), the polyimide precursor composition can be endowed with developing function and good adhesive strength. Furthermore, by using a polyimide precursor containing a nitrogen-containing heterocyclic group, a polyimide precursor composition can be provided that has developing function and can form a polyimide layer with good adhesive strength and high precision, even without using benzotriazole (BTA).

[0131] As can be seen from the above experimental data, the polyimide precursor composition of the present disclosure has a developing function, and the insulating layer formed on a substrate using the polyimide precursor composition of the present disclosure has superior adhesion to the substrate. Furthermore, the use of the polyimide precursor composition of the present disclosure enables the formation of a polyimide layer with higher precision.

[0132] The features of the above-described embodiments can help those skilled in the art to better understand the present invention. Furthermore, those skilled in the art will understand that other manufacturing processes and structures can be designed and modified based on the present invention to achieve the same purpose and / or advantages. Furthermore, those skilled in the art will understand that these equivalent replacements do not depart from the spirit and scope of the present invention, and that changes, substitutions, or modifications are possible without departing from the spirit and scope of the present invention. [Explanation of symbols]

[0133] S101~S107...Step 201... Circuit board 203...Polyimide precursor layer 205...Polyimide layer 207...insulating layer

Claims

1. 1. A polyimide precursor composition comprising: a polyimide precursor; an additive compound; The additive compound is a first functional group selected from a trialkoxysilyl group or a nitrogen-containing heterocyclic group; a second functional group selected from a (meth)acrylate group, a nitrogen-containing heterocyclic group, or an amino group; The polyimide precursor is (1) a first polyimide precursor having structural units derived from a diamine monomer having a silicon-oxygen-silicon group (—Si—O—Si—) or an acrylic acid group; (2) a second polyimide precursor having a terminal amino group substituted with a nitrogen-containing heterocyclic group; (3) a third polyimide precursor modified with a compound having an isocyanate group (—NCO); one or a combination thereof selected from A polyimide precursor composition, wherein at least one of the polyimide precursor and / or the additive compound comprises a nitrogen-containing heterocyclic group.

2. 2. The polyimide precursor composition according to claim 1, wherein the nitrogen-containing heterocyclic group contained in at least one of the polyimide precursor and the additive compound is an aziridinyl group, a piperidinyl group, a pyrazolyl group, a morpholinyl group, a tetrazolyl group, a triazolyl group, an imidazolyl group, a benzotriazolyl group, or a benzimidazolyl group.

3. 2. The polyimide precursor composition of claim 1, wherein the first polyimide precursor is a hydroxyalkyl (meth)acrylate-modified polyimide precursor.

4. 4. The polyimide precursor composition of claim 3, wherein the structural units of the first polyimide precursor are derived from (1,3-bis(3-aminopropyl)tetramethyldisiloxane) (APDS) or (2-(methacryloyloxy)ethyl 3,5-diaminobenzoate) (ES-HEMA).

5. 2. The polyimide precursor composition according to claim 1, wherein the amino group terminal of the second polyimide precursor is derived from 5-aminotetrazole (5-ATZ).

6. 2. The polyimide precursor composition according to claim 1, wherein the compound having an isocyanate (—NCO) group includes 3-(triethoxysilyl)propyl isocyanate, diethoxy(3-isocyanatopropyl)silane, or ethoxy(3-isocyanatopropyl)silane.

7. 10. The polyimide precursor composition of claim 1, wherein the polyimide precursor composition is free of benzotriazole (BTA).

8. 2. The polyimide precursor composition according to claim 1, wherein the additive compound is selected from 3-(methacryloxy)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, X-12-1214A (purchased from Shin-Etsu Chemical Co., Ltd.), TC-7902-02 (purchased from Kanliang Enterprise Co., Ltd.), or a combination thereof.

9. 2. The polyimide precursor composition according to claim 1, wherein the polyimide precursor composition contains 0.001 parts by weight or more and 2 parts by weight or less of the additive compound, based on 100 parts by weight of the polyimide precursor.

10. A method for producing a polyimide precursor composition, comprising: providing a polyimide precursor; mixing an additive compound with the polyimide precursor to form the polyimide precursor composition; Including, The additive compound is a first functional group selected from a trialkoxysilyl group or a nitrogen-containing heterocycle; a second functional group selected from a (meth)acrylate group, a nitrogen-containing heterocyclic group, or an amino group; The polyimide precursor is (1) a first polyimide precursor having structural units derived from a diamine monomer having a silicon-oxygen-silicon or acrylic acid group; (2) a second polyimide precursor having a terminal amino group substituted with a nitrogen-containing heterocyclic group; or (3) a third polyimide precursor modified with a compound having an isocyanate group (—NCO); One or a combination thereof is selected from and wherein at least one of the polyimide precursor and the additive compound contains a nitrogen-containing heterocyclic group.

11. 11. The method for producing a polyimide precursor composition according to claim 10, wherein the first polyimide precursor is formed by polymerizing a diamine monomer having a silicon-oxygen-silicon group or an acrylic acid group and a diacid anhydride monomer.

12. 11. The method for producing a polyimide precursor composition according to claim 10, wherein the second polyimide precursor is formed by polymerizing a diamine monomer, a diacid anhydride monomer, and an amino group compound having a nitrogen-containing heterocyclic group.

13. 11. The method for producing a polyimide precursor composition according to claim 10, wherein the third polyimide precursor is formed by polymerizing a first diamine monomer, a second diamine monomer, and a diacid anhydride monomer, followed by modifying the polymerized product with a compound having an isocyanate group, and the second diamine monomer has a hydroxy group.

14. 10. Use of the polyimide precursor composition according to any one of claims 1 to 9 for forming an insulating layer on a substrate.

15. A method for forming an insulating layer on a substrate using the polyimide precursor composition according to any one of claims 1 to 9, comprising the steps of: mixing the polyimide precursor composition and a solvent to form a polyimide precursor varnish; applying the polyimide precursor varnish onto a substrate to form a polyimide precursor layer; performing an exposure process on the polyimide precursor layer to form a polyimide layer; performing a post-bake process on the polyimide layer; A method comprising:

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