Photosensitive resin composition, insulating film, and semiconductor device

Abstract

The present disclosure relates to a photosensitive resin composition, and provides a photosensitive resin composition which is soluble in an environmentally friendly aqueous solvent, can be developed with an aqueous developing solution, and can provide an insulating film having excellent chemical resistance, low dielectric constant characteristics, low dielectric loss characteristics, and mechanical characteristics.

Description

Technical Field

[0001] The present disclosure relates to a photosensitive resin composition, an insulating film, and a semiconductor device.

[0002] The present disclosure claims priority to and the benefit of Korean Patent Application No. 10-2023-0061852 filed in the Korean Intellectual Property Office on May 12, 2023, the entire contents of which are incorporated herein by reference. Background Art

[0003] For surface protection films, interlayer insulating films, etc. of semiconductor elements of electronic devices, polyimide-based resins and polybenzoic acid-based resins having excellent heat resistance and mechanical properties are widely used in the art. When a film containing these resins is formed, by mixing a polyimide precursor or a polybenzoic acid When the coating film of the azole precursor is thermally dehydrated and ring-closed to obtain a thin film having excellent heat resistance and mechanical properties, a high-temperature heat treatment of about 350° C. is generally required.

[0004] However, in order to respond to recent demands such as heat load reduction or low warping of devices, a polyimide-based resin or a polybenzoic acid-based resin curable by heat treatment at a low temperature of about 250° C. or less, more preferably 200° C. or less is required. Azole resin. Summary of the invention

[0005] Technical issues

[0006] The present disclosure is intended to provide a photosensitive resin composition that is soluble in an environmentally friendly aqueous solvent, developable with an aqueous developing solution, and capable of providing an insulating film having excellent chemical resistance, low dielectric constant characteristics, low dielectric loss characteristics, and mechanical characteristics.

[0007] However, objects to be achieved by the present disclosure are not limited to the above objects, and other objects not mentioned will be clearly understood by those skilled in the art from the following description.

[0008] Technical Solution

[0009] One embodiment of the present disclosure provides a photosensitive resin composition including a polyimide containing repeating units represented by the following Chemical Formulas 1 to 4, wherein a ratio of a total number of -F functional groups to a total number of -OH functional groups contained in the repeating units represented by Chemical Formulas 1 to 4 satisfies 2≤-F / -OH≤5:

[0010] [Chemical formula 1]

[0011]

[0012] [Chemical formula 2]

[0013]

[0014] [Chemical formula 3]

[0015]

[0016] [Chemical formula 4]

[0017]

[0018] In Chemical Formulae 1 to 4,

[0019] A1 is a tetravalent aliphatic organic group; A2 is a tetravalent aromatic ring group; B1 is a divalent aromatic ring group; B2 is a flexible functional group; p1 to p4 are each independently an integer from 1 to 10,000; and at least one of A1, A2, B1 and B2 contains a -F functional group, a -OH functional group, or a -F functional group and a -OH functional group.

[0020] Furthermore, another embodiment of the present application provides an insulating film including the photosensitive resin composition or a cured product thereof.

[0021] Furthermore, another embodiment of the present application provides a semiconductor device including the insulating film.

[0022] Beneficial Effects

[0023] The photosensitive resin composition according to one embodiment of the present disclosure includes a polyimide including a repeating unit represented by Chemical Formula 1 to Chemical Formula 4, and since the ratio of the total number of -F functional groups to the total number of -OH functional groups included in the repeating units represented by Chemical Formula 1 to Chemical Formula 4 satisfies 2≤-F / -OH≤5, the composition has the advantages of being easily soluble in propylene glycol monomethyl ether acetate (PGMEA) (an environmentally friendly aqueous solvent) and the like, and being developable with TMAH (tetramethylammonium hydroxide) (an aqueous developing solution) and the like.

[0024] Specifically, in order to make the photosensitive resin composition easily soluble in PGMEA (an environmentally friendly aqueous solvent) and developable with TMAH (an aqueous developing solution), -F and -OH functional groups are required, however, as the -F and -OH functional groups increase, there are disadvantages in that properties such as dielectric loss (Df) and elongation deteriorate and chemical resistance also deteriorates.

[0025] However, the photosensitive resin composition according to one embodiment of the present disclosure includes a polyimide containing a repeating unit represented by Chemical Formula 1 to Chemical Formula 4, and since the ratio of the total number of -F functional groups contained in the repeating units represented by Chemical Formula 1 to Chemical Formula 4 to the total number of -OH functional groups satisfies 2≤-F / -OH≤5, the composition has the advantages of being easily soluble in PGMEA (an environmentally friendly aqueous solvent) and being developable with TMAH (an aqueous developing solution), and can provide an insulating film having excellent low dielectric constant characteristics, low dielectric loss characteristics, mechanical properties such as elongation, and chemical resistance.

[0026] The effects of the present disclosure are not limited to the above-mentioned effects, and unmentioned effects will be clearly understood by those skilled in the art from the present specification and the accompanying drawings. DETAILED DESCRIPTION

[0027] In the present specification, unless specifically described to the contrary, a description that a part “includes” certain constituent elements means that it may further include other constituent elements, and does not exclude other constituent elements.

[0028] Throughout this specification, description that a certain member is placed “on” another member includes not only a case where the certain member is in contact with the other member but also a case where another member exists between the two members.

[0029] Throughout the present specification, the unit "parts by weight" may mean a weight ratio between components.

[0030] In this specification, terms including ordinal numbers such as "first" and "second" are used for the purpose of distinguishing one constituent element from another constituent element and are not limited by the ordinal numbers. For example, within the scope of the present disclosure, the first constituent element may also be referred to as the second constituent element, and similarly, the second constituent element may be referred to as the first constituent element.

[0031] Throughout the present specification, the unit "part by mole" may mean a molar ratio between components.

[0032] Throughout the present specification, "(meth)acrylate" is used to collectively mean acrylate and methacrylate.

[0033] In the present specification, "polymer" means a compound formed by repeating a repeating unit (basic unit). The polymer may be represented as a polymer or a compound formed of a polymer.

[0034] Throughout this specification, the "weight average molecular weight" and "number average molecular weight" of a compound can be calculated using the molecular weight and molecular weight distribution of the compound. Specifically, tetrahydrofuran (THF) and the compound are introduced into a 1 ml glass vial to prepare a sample with a compound concentration of 1 wt %, and after filtering the standard (polystyrene) and the sample through a filter (pore size of 0.45 μm), they are injected into a GPC syringe, and the elution time of the sample can be compared with the calibration curve of the standard to obtain the molecular weight and molecular weight distribution of the compound. In this article, Infinity II1260 (Agilient) can be used as a measuring device, and the flow rate can be set to 1.00 mL / min, and the column temperature can be set to 40.0 ° C.

[0035] Throughout this specification, the term "substituted" means that another functional group is bonded to replace a hydrogen atom in a compound, and the position of substitution is not limited as long as it is a position where a hydrogen atom is replaced (i.e., a position that a substituent can replace), and when two or more substituents are substituted, the two or more substituents may be the same as or different from each other.

[0036] In the present specification, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the following: deuterium; halogen group; cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amide group; primary amino group; carboxyl group; sulfonic acid group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; alkylthio group; arylthio group; alkylsulfonyl group; arylsulfonyl group; silyl group; boron group; alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; alkylaryl group; alkoxysilylalkyl group; arylphosphino group; or a heterocyclic group containing one or more of N, O and S atoms, or substituted or unsubstituted with a substituent connected with two or more of the substituents exemplified above. For example, "a substituent in which two or more substituents are connected" can be a biphenyl group. In other words, the biphenyl group can be an aryl group, or it can also be interpreted as a substituent in which two phenyl groups are connected.

[0037] Throughout the specification, "aliphatic cyclic group" or "aromatic cyclic group" may be interpreted as a single ring existing alone; or two or more rings linked together to form a condensed ring; or two or more rings linked by a direct bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O)2-, -OCO-, -Si(CH3)2-, or a substituted or unsubstituted alkylene group.

[0038] Throughout this manual, It indicates the part to which the corresponding group is connected to another adjacent atom.

[0039] Throughout this specification, "-F" means a fluorine functional group contained in a compound, and "-OH" means a hydroxyl functional group contained in a compound.

[0040] Throughout this specification, -F / -OH (the ratio of the number of -F functional groups contained in a polymer or a repeating unit to the number of -OH functional groups) means a value calculated by dividing the total molar number of -F functional groups contained in the monomers used to polymerize the polymer or the repeating unit by the total molar number of -OH functional groups.

[0041] Hereinafter, the present disclosure will be described in more detail.

[0042] [Photosensitive resin composition]

[0043] One embodiment of the present disclosure provides a photosensitive resin composition including a polyimide containing repeating units represented by the following Chemical Formulas 1 to 4, wherein a ratio of a total number of -F functional groups to a total number of -OH functional groups contained in the repeating units represented by Chemical Formulas 1 to 4 satisfies 2≤-F / -OH≤5:

[0044] [Chemical formula 1]

[0045]

[0046] [Chemical formula 2]

[0047]

[0048] [Chemical formula 3]

[0049]

[0050] [Chemical formula 4]

[0051]

[0052] In Chemical Formulae 1 to 4,

[0053] A1 is a tetravalent aliphatic organic group; A2 is a tetravalent aromatic ring group; B1 is a divalent aromatic ring group; B2 is a flexible functional group; p1 to p4 are each independently an integer from 1 to 10,000; and at least one of A1, A2, B1 and B2 contains a -F functional group, a -OH functional group, or a -F functional group and a -OH functional group.

[0054] Generally, the polyimide included in the photosensitive resin composition needs to include -F and -OH functional groups so as to be easily soluble in PGMEA (an environmentally friendly aqueous solvent) and developable with TMAH (an aqueous developing solution).

[0055] However, when the included -F and -OH functional groups are increased in order to make polyimide easily soluble in PGMEA (an environmentally friendly aqueous solvent) and developable with TMAH (an aqueous developing solution), there are disadvantages in that characteristics such as dielectric loss (Df) and elongation are deteriorated and chemical resistance is also deteriorated.

[0056] The -F functional group has advantages in solubility and low dielectric loss characteristics, but when contained in an excessive amount, the dielectric loss may be large and the film characteristics may be degraded. The -OH functional group has advantages in development and solubility, but when the content is increased, it may cause poor results in reliability and the like due to its high hygroscopicity.

[0057] Since the ratio of the total number of -F functional groups contained in the repeating units represented by Chemical Formula 1 to Chemical Formula 4 to the total number of -OH functional groups satisfies 2≤-F / -OH≤5, the photosensitive resin composition according to one embodiment of the present disclosure has the advantages of being easily soluble in PGMEA (an environmentally friendly aqueous solvent) and being developable with TMAH (an aqueous developing solution). In addition, at the same time, a photosensitive resin composition having low dielectric loss (Df) and dielectric constant (Dk), excellent mechanical properties such as elongation, and also excellent chemical resistance can be provided.

[0058] According to one embodiment of the present disclosure, the polyimide may include a terminal portion derived from a capping compound described later.

[0059] According to one embodiment of the present disclosure, the photosensitive resin composition may be a positive photosensitive resin composition or a negative photosensitive resin composition.

[0060] According to one embodiment of the present disclosure, the weight average molecular weight of polyimide can be 1,000g / mol to 70,000g / mol. More preferably, the weight average molecular weight of polyimide can be 5,000g / mol to 50,000g / mol, 10,000g / mol to 70,000g / mol, 10,000g / mol to 50,000g / mol, 15,000g / mol to 50,000g / mol, 15,000g / mol to 40,000g / mol or 20,000g / mol to 40,000g / mol. When the weight average molecular weight of polyimide resin is less than 1,000g / mol, the insulating film produced may become brittle and have poor adhesive strength. In addition, polyimide resins having a weight average molecular weight greater than 70,000g / mol are not preferred because the composition may not be developed due to reduced sensitivity, or residual scum may remain.

[0061] The -F / -OH ratio preferably satisfies 2.1 or more, more preferably satisfies 2.5 or more, and even more preferably satisfies 3.0 or more. In addition, the -F / -OH ratio preferably satisfies 4.8 or less, more preferably satisfies 4.5 or less or 4.3 or less, and even more preferably satisfies 4.0 or less.

[0062] When the -F / -OH ratio is less than 2, there are problems of increased dielectric loss value due to increased hygroscopicity, decreased chemical resistance, and decreased reliability due to a relatively high -OH functional group ratio.

[0063] Meanwhile, when the -F / -OH ratio is greater than 5, there are problems in that dielectric loss increases and mechanical properties and chemical resistance of the film decrease.

[0064] The repeating unit represented by Chemical Formula 1 comprises A1 (the aliphatic portion derived from the aliphatic dianhydride monomer) and B1 (the aromatic portion derived from the diamine monomer not containing a flexible functional group), and the repeating unit represented by Chemical Formula 2 comprises A2 (the aromatic portion derived from the aromatic dianhydride monomer) and B1 (the aromatic portion derived from the diamine monomer not containing a flexible functional group), the repeating unit represented by Chemical Formula 3 comprises A1 (the aliphatic portion derived from the aliphatic dianhydride monomer) and B2 (the flexible portion derived from the diamine monomer containing a flexible functional group), and the repeating unit represented by Chemical Formula 4 comprises A2 (the aromatic portion derived from the aromatic dianhydride monomer) and B2 (the flexible portion derived from the diamine monomer containing a flexible functional group).

[0065] A general photosensitive resin composition includes a polymer of an aromatic dianhydride monomer and a diamine monomer without a flexible functional group, however, a photosensitive resin composition according to an embodiment of the present disclosure uses an aliphatic dianhydride monomer introduced with an aliphatic portion to reduce a dielectric loss value, and uses a diamine monomer including a flexible functional group to increase elongation.

[0066] However, when the aliphatic portion included in polyimide to reduce the dielectric loss value and the flexible portion included in polyimide to increase the elongation are included beyond the appropriate content range, the characteristics of the photosensitive resin composition may be degraded, and these portions need to be included in an appropriate ratio.

[0067] Specifically, the photosensitive resin composition according to one embodiment of the present disclosure has the advantages of being easily soluble in PGMEA (an environmentally friendly aqueous solvent) and developable with TMAH (an aqueous developing solution), and in order to provide a photosensitive resin composition having excellent properties such as dielectric loss and elongation as well as excellent chemical resistance, the polyimide containing the repeating units represented by Chemical Formula 1 to Chemical Formula 4 contains an aliphatic portion and a flexible portion in an appropriate amount.

[0068] According to one embodiment of the present disclosure, a ratio of the total number of repeating units represented by Chemical Formula 1 and Chemical Formula 3 relative to the total number of repeating units represented by Chemical Formula 2 and Chemical Formula 4 may satisfy 0.01 to 1.0.

[0069] Since the ratio of the total number of repeating units represented by Chemical Formula 1 and Chemical Formula 3 to the total number of repeating units represented by Chemical Formula 2 and Chemical Formula 4 satisfies 0.01 to 1.0, the content of the aliphatic part contained in the polyimide is appropriate, and as a result, the photosensitive resin composition is easily soluble in PGMEA (an environmentally friendly aqueous solvent) and can be developed with TMAH (an aqueous developing solution), and at the same time, can have a low dielectric loss (D f )value.

[0070] More specifically, the ratio of the total number of repeating units represented by Chemical Formula 1 and Chemical Formula 3 to the total number of repeating units represented by Chemical Formula 2 and Chemical Formula 4 preferably satisfies 0.01 or more, more preferably satisfies 0.05 or more, and even more preferably satisfies 0.1 or more. In addition, the ratio of the total number of repeating units represented by Chemical Formula 1 and Chemical Formula 3 to the total number of repeating units represented by Chemical Formula 2 and Chemical Formula 4 preferably satisfies 1.0 or less, more preferably satisfies 0.9 or less or 0.8 or less, and even more preferably satisfies 0.7 or less.

[0071] When the ratio of the total number of repeating units represented by Chemical Formula 1 and Chemical Formula 3 to the total number of repeating units represented by Chemical Formula 2 and Chemical Formula 4 is less than 0.01, it is difficult to dissolve the composition in PGMEA (an environmentally friendly aqueous solvent), or the developability with TMAH (aqueous developing solution) may be reduced, and when the ratio is greater than 1.0, the dielectric loss characteristics may be reduced.

[0072] According to one embodiment of the present disclosure, the ratio of the total number of repeating units represented by Chemical Formula 1 and Chemical Formula 3 to the total number of repeating units represented by Chemical Formula 1 to Chemical Formula 4 may be 0.05 to 0.5. By satisfying the above ratio, a photosensitive resin composition that is easily soluble in PGMEA (an environmentally friendly aqueous solvent), developable with TMAH (an aqueous developing solution), and at the same time has a low dielectric loss value may be obtained.

[0073] When the ratio of the total number of repeating units represented by Chemical Formula 1 and Chemical Formula 3 to the total number of repeating units represented by Chemical Formula 1 to Chemical Formula 4 is less than 0.05, it is difficult to dissolve the composition in PGMEA (an environmentally friendly aqueous solvent), or the developability with TMAH (aqueous developing solution) may be reduced, and when the ratio is greater than 0.5, the dielectric loss characteristics may be reduced.

[0074] According to one embodiment of the present disclosure, a ratio of the total number of repeating units represented by Chemical Formula 3 and Chemical Formula 4 relative to the total number of repeating units represented by Chemical Formula 1 to Chemical Formula 4 may be 0.05 to 0.5.

[0075] When the ratio of the total number of repeating units represented by Chemical Formula 3 and Chemical Formula 4 relative to the total number of repeating units represented by Chemical Formula 1 to Chemical Formula 4 satisfies 0.05 to 0.5, the content of the flexible part contained in the polyimide is appropriate, and as a result, a photosensitive resin composition that is easily soluble in PGMEA (an environmentally friendly aqueous solvent), developable with TMAH (aqueous developing solution), and simultaneously has excellent adhesion as well as excellent elongation and chemical resistance properties can be obtained.

[0076] When the ratio of the total number of repeating units represented by Chemical Formula 3 and Chemical Formula 4 to the total number of repeating units represented by Chemical Formula 1 to Chemical Formula 4 is less than 0.05, it is difficult to dissolve the composition in PGMEA (an environmentally friendly aqueous solvent), and problems such as reduced developability with TMAH (aqueous developing solution) and reduced adhesion may occur, and when the ratio is greater than 0.5, elongation and chemical resistance characteristics may decrease.

[0077] According to one embodiment of the present disclosure, the tetravalent aliphatic organic group (A1) may include one or more types selected from the group consisting of a substituted or unsubstituted aliphatic cyclic group, the following Chemical Formula 5, and the following Chemical Formula 6.

[0078] [Chemical formula 5]

[0079]

[0080] [Chemical formula 6]

[0081]

[0082] In Chemical Formula 5 and Chemical Formula 6, L1 is a direct bond; a substituted or unsubstituted alkylene group; -O-; -SO2-; -CO-; or -OCO-, R1 to R6 are the same as or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; or a carboxyl group, m and n are 2, R5 are the same as or different from each other, and R6 are the same as or different from each other.

[0083] More specifically, the tetravalent aliphatic organic group (A1) may include one or more types selected from the following chemical formulae.

[0084]

[0085] According to one embodiment of the present disclosure, the tetravalent aromatic ring group (A2) may include one or more types selected from a substituted or unsubstituted tetravalent aromatic monocyclic ring and the following Chemical Formula 7.

[0086] [Chemical formula 7]

[0087]

[0088] In Chemical Formula 7, L2 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO2-; -CO-; or -OCO-, R1 and R2 are the same as or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; or a carboxyl group, m and n are the same as or different from each other and are each independently an integer from 0 to 3, when m is 2 or greater, R1 are the same as or different from each other, and when n is 2 or greater, R2 are the same as or different from each other.

[0089] According to one embodiment of the present disclosure, the divalent aromatic ring group (B1) may include one or more types selected from a substituted or unsubstituted divalent aromatic monocyclic ring, the following Chemical Formula 8, and the following Chemical Formula 9.

[0090] [Chemical formula 8]

[0091]

[0092] [Chemical formula 9]

[0093]

[0094] In Chemical Formula 8 and Chemical Formula 9, L3 and L4 are the same as or different from each other and are each independently a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO2-; -CO-; or -OCO-, R1 to R4 are the same as or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a hydroxyl group; or a substituted or unsubstituted amine group, m1, m2, n1 and n2 are the same as or different from each other and are each independently an integer from 0 to 4, when m1 is 2 or greater, R1 is the same as or different from each other, when n1 is 2 or greater, R2 is the same as or different from each other, when m2 is 2 or greater, R3 is the same as or different from each other, and when n2 is 2 or greater, R4 is the same as or different from each other.

[0095] According to one embodiment of the present disclosure, the flexible functional group (B2) may include one or more types selected from the following Chemical Formula 10 to Chemical Formula 13.

[0096] [Chemical formula 10]

[0097]

[0098] [Chemical formula 11]

[0099]

[0100] [Chemical formula 12]

[0101]

[0102] [Chemical formula 13]

[0103]

[0104] In Chemical Formulae 9 to 12, X1 to X3 are the same as or different from each other and are each independently -O-; or -CH2-, La1 to La11 are the same as or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group, R1 to R6 are the same as or different from each other and are each independently hydrogen; or a substituted or unsubstituted alkyl group, x, y and z are each independently a real number ranging from 0 to 50, and a1 is a real number ranging from 1 to 30.

[0105] More specifically, the flexible functional group (B2) may include one or more types selected from the following chemical formulae.

[0106]

[0107]

[0108] In the chemical formula, each n is independently a real number of 1 to 30, and x, y and z are each independently a real number of 1 to 50.

[0109] [Monomers for polyimide synthesis]

[0110] In the polyimide containing the repeating units represented by Chemical Formula 1 to Chemical Formula 4, each repeating unit may be obtained by reacting a dianhydride with a diamine. More specifically, the dianhydride may be a tetracarboxylic dianhydride.

[0111] Specifically, the repeating unit represented by Chemical Formula 1 can be obtained by reacting an aliphatic dianhydride monomer with a diamine monomer not containing a flexible functional group, the repeating unit represented by Chemical Formula 2 can be obtained by reacting an aromatic dianhydride monomer with a diamine monomer not containing a flexible functional group, the repeating unit represented by Chemical Formula 3 can be obtained by reacting an aliphatic dianhydride monomer with a diamine monomer containing a flexible functional group, and the repeating unit represented by Chemical Formula 4 can be obtained by reacting an aromatic dianhydride monomer with a diamine monomer containing a flexible functional group.

[0112] Aliphatic dianhydride monomer

[0113] According to one embodiment of the present disclosure, the aliphatic dianhydride monomer may include one or more types selected from the following Chemical Formula 14 to Chemical Formula 16.

[0114] [Chemical formula 14]

[0115]

[0116] [Chemical formula 15]

[0117]

[0118] [Chemical formula 16]

[0119]

[0120] In Chemical Formulae 14 to 16, Cy1 is a substituted or unsubstituted aliphatic monocyclic ring, L1 is a direct bond; a substituted or unsubstituted alkylene group; -O-; -SO2-; -CO-; or -OCO-, Ra to Rd are the same as or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; or a carboxyl group, m and n are the same as or different from each other and are each independently an integer from 0 to 3, when m is 2 or greater, Ra are the same as or different from each other, and when n is 2 or greater, Rb are the same as or different from each other.

[0121] More specifically, the aliphatic dianhydride monomer may include one or more types selected from the following chemical formulae.

[0122]

[0123] According to one embodiment of the present disclosure, the aliphatic dianhydride monomer may include an aliphatic dianhydride monomer containing a substituted or unsubstituted alkyl group and an aliphatic dianhydride monomer containing a substituted or unsubstituted aliphatic ring. When the aliphatic dianhydride monomer includes these two monomers, the photosensitive resin composition containing the polyimide polymerized therefrom has the advantages of being easily soluble in PGMEA (an environmentally friendly aqueous solvent) and being developable with TMAH (an aqueous developing solution), and at the same time, having excellent film properties due to reduced dielectric loss (Df), and also having excellent chemical resistance.

[0124] Aromatic dianhydride monomer

[0125] According to one embodiment of the present disclosure, the aromatic dianhydride monomer may include one or more types selected from the following Chemical Formula 17 and Chemical Formula 18.

[0126] [Chemical formula 17]

[0127]

[0128] [Chemical formula 18]

[0129]

[0130] In Chemical Formula 17 and Chemical Formula 18, Cy2 is a substituted or unsubstituted aromatic ring group, L2 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO2-; -CO-; or -OCO-, Ra and Rb are the same as or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; or a carboxyl group, m and n are the same as or different from each other and are each independently an integer from 0 to 3, when m is 2 or greater, Ra are the same as or different from each other, and when n is 2 or greater, Rb are the same as or different from each other.

[0131] According to one embodiment of the present disclosure, the aromatic dianhydride monomer may include one or more types selected from the following chemical formulae, but is not limited thereto.

[0132]

[0133] Diamine monomers not containing flexible functional groups

[0134] According to one embodiment of the present disclosure, the diamine monomer not including a flexible functional group may include one or more types selected from the following Chemical Formula 19 to Chemical Formula 21.

[0135] [Chemical formula 19]

[0136]

[0137] [Chemical formula 20]

[0138]

[0139] [Chemical formula 21]

[0140]

[0141] In Chemical Formulae 19 to 21, L3 and L4 are the same as or different from each other and are each independently a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO2-; -CO-; or -OCO-, Ra to Re are the same as or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a hydroxyl group; or a substituted or unsubstituted amine group, m1, m2, m3, n2 and n3 are the same as or different from each other and are each independently an integer from 0 to 4, when m1 is 2 or greater, Ra is the same as or different from each other, when m2 is 2 or greater, Rb is the same as or different from each other, when m3 is 2 or greater, Rd is the same as or different from each other, when n2 is 2 or greater, Rc is the same as or different from each other, and when n3 is 2 or greater, Re is the same as or different from each other.

[0142] Diamine monomers containing flexible functional groups

[0143] According to one embodiment of the present disclosure, the diamine monomer including a flexible functional group may have an amine group bonded to each end of the flexible functional group.

[0144] Specifically, the amine group may be bonded to both ends of any one flexible functional group selected from Chemical Formula 10 to Chemical Formula 13 or a flexible functional group in which two or more types thereof are bonded to each other.

[0145] End-capping compounds

[0146] According to one embodiment of the present disclosure, a polyimide polymerized from a dianhydride monomer and a diamine monomer may be capped with a capping compound.

[0147] According to one embodiment of the present disclosure, the capping compound may be a monoamine compound including one amine group, a monoanhydride compound, or a mixture thereof.

[0148] For example, the end-capping compound may be trimellitic anhydride, phthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 3-aminophenol (3AP), or a mixture thereof.

[0149] [additive]

[0150] According to one embodiment of the present disclosure, the photosensitive resin composition may further include one or more types selected from photosensitizers, crosslinkers, antioxidants, surfactants, and solvents. In addition, the photosensitive resin composition may further include additives known in the art according to the application.

[0151] The photosensitizer may include a photoacid generator, or a combination of a photopolymerization initiator and a compound having two or more ethylenically unsaturated bonds. By including a photoacid generator, an acid is generated in the light-irradiated portion, thereby increasing the solubility of the light-irradiated portion in an alkaline aqueous solution, and thus, a positive concave-convex pattern in which the light-irradiated portion is dissolved can be obtained. In addition, by including a photoacid generator and an epoxy compound or a cross-linking agent, the acid generated in the light-irradiated portion accelerates the cross-linking reaction of the epoxy compound or the cross-linking agent, and thus, a negative concave-convex pattern in which the light-irradiated portion becomes insoluble can also be obtained. In addition, by including a photopolymerization initiator and a compound having two or more ethylenically unsaturated bonds, the active free radicals generated in the light-irradiated portion undergo free radical polymerization of ethylenically unsaturated bonds, and thus, a negative concave-convex pattern in which the light-irradiated portion becomes insoluble can also be obtained.

[0152] The photoacid generator may include quinone diazide compounds, sulfonium salts, Salt, diazonium salt, iodine Salt, etc.

[0153] The quinonediazide compound may include a compound in which the sulfonic acid of a quinonediazide ester is bonded to a polyhydroxy compound, a compound in which the sulfonic acid of a quinonediazide sulfonamide is bonded to a polyamino compound, a compound in which the sulfonic acid of a quinonediazide ester is bonded to and / or the sulfonamide is bonded to a polyhydroxy polyamino compound, etc. Preferably, 50 mol% or more of all functional groups of these polyhydroxy compounds or polyamino compounds are substituted with quinonediazide. By replacing 50 mol% or more of the functional groups with quinonediazide, the solubility of the resin film in an alkaline developing solution becomes favorable in the exposed area, and there is an advantage of obtaining a fine pattern with a high contrast with the unexposed area. In addition, it is preferred to contain two or more types of photoacid generators, and therefore, a heat-resistant resin composition having a highly sensitive photosensitive property can be obtained.

[0154] As the quinonediazide compound, all compounds having a 5-naphthoquinonediazidesulfonyl group and compounds having a 4-naphthoquinonediazidesulfonyl group can be preferably used. The 4-naphthoquinonediazidesulfonyl ester compound has absorption in the i-line region of a mercury lamp and is therefore suitable for i-line exposure. The 5-naphthoquinonediazidesulfonyl ester compound has absorption up to the g-line region of a mercury lamp and is therefore suitable for g-line exposure. Depending on the exposure wavelength, a 4-naphthoquinonediazidesulfonyl ester compound or a 5-naphthoquinonediazidesulfonyl ester compound is preferably selected. In addition, a naphthoquinonediazidesulfonyl ester compound having a 4-naphthoquinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group in the same molecule may be contained, or both a 4-naphthoquinonediazidesulfonyl ester compound and a 5-naphthoquinonediazidesulfonyl ester compound may be contained.

[0155] Preferred sulfonium salts, Onium salts and diazonium salts are used as photoacid generators because they appropriately stabilize the acid component generated by exposure. Among them, sulfonium salts are preferred. If necessary, a sensitizer or the like may also be included.

[0156] The photopolymerization initiator may include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl-phenyl ketone, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, o-methyl-benzoylbenzoate, 4-phenyldimethoxybenzoate, Benzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzyl ammonium bromide, (4-benzoylbenzyl)trimethylammonium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propenyl ammonium chloride monohydrate, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N, N,N-trimethyl-1-propylammonium chloride, 2,4,6-trimethylbenzoylphenylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2-(o-benzoyloxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(o-acetyloxime), 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxylate, η5-cyclopentadienyl-η6-cumyl-iron (1+)-hexafluorophosphate (1-), diphenyl sulfide derivatives, bis(η5-2,4-cyclopentadien-1-yl) -bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl-4-methylphenyl ketone, dibenzyl ketone, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyldichloroacetophenone, benzylmethoxyethyl acetal, anthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthraquinone, benzanthrone, dibenzosuberone, methylene anthraquinone, 4-azidobenzylideneacetophenone, 2,6-bis(p-azidobenzylidene)cyclohexane, 2,6-bis(p-azidobenzylidene)-4-methylcyclohexanone, 2-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, benzothiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylsulfone, benzoyl peroxide, etc., or a combination of a photoreducible dye (e.g., eosin or methylene blue) and a reducing agent (e.g., ascorbic acid or triethanolamine), etc. Two or more types thereof may be included. ,

[0157] The content of the photosensitizer is preferably 0.05 to 50 parts by weight relative to 100 parts by weight of the polyimide. When the photosensitizer is a photoacid generator, from the viewpoint of high sensitivity, the content is preferably 0.01 to 50 parts by weight relative to 100 parts by weight of the polyimide. The content of the quinone diazide compound in the photoacid generator is preferably 3 to 40 parts by weight. In addition, regarding sulfonium salts, The content of the salt and the diazonium salt is preferably 0.5 to 20 parts by weight relative to 100 parts by weight of the polyimide. This content range is preferred because sufficient acid is generated by light irradiation and the sensitivity is improved. In addition, it is preferred that the content of the photoacid generator is 20 parts by weight or less because no development pattern residue is generated.

[0158] The content of the photopolymerization initiator is preferably 0.1 to 20 parts by weight relative to 100 parts by weight of the polyimide. When the content is 0.1 parts by weight or more, sufficient free radicals are generated by light irradiation, and sensitivity is improved. In addition, when the content is 20 parts by weight or less, the unirradiated portion will not be cured due to excessive generation of free radicals, and alkaline developability is improved. Relative to 100 parts by weight of the polyimide, the content of the compound having two or more ethylenically unsaturated bonds is preferably 5 to 50 parts by weight. A content of 5 parts by weight or more is preferred because a cured resin film with high mechanical properties is obtained by crosslinking. A content of 50 parts by weight or less is preferred because sensitivity is not impaired.

[0159] The cross-linking agent is not particularly limited, and those used in the art can be used without restriction. For example, as a cross-linking agent, a thermal cross-linking agent or a free radical monomer can be used. More specifically, as a cross-linking agent, a compound having at least two alkoxymethyl groups and / or methylol groups, and a compound having at least two epoxy groups and / or oxetane groups can be used, however, the cross-linking agent is not limited thereto. By including these compounds, a condensation reaction occurs with the polyimide resin during the baking after patterning to form a cross-linked structure, and the mechanical properties of the cured resin pattern, such as elongation, can be improved. In addition, two or more types of cross-linking agents can be used, which enables a wider design range.

[0160] Preferred examples of the compound having at least two alkoxymethyl groups and / or hydroxymethyl groups may include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DMLMBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM, which are commercially available from various companies. -PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOMBPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA and HMOM-TPHAP (in the above, trade names, manufactured by Honshu Chemical Industry Co., Ltd.), and NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM and NIKALAC MX-750LM (in the above, trade names, manufactured by Sanwa Chemical Co., Ltd.). Two or more types thereof may be included.

[0161] In addition, preferred examples of compounds having at least two epoxy groups and / or oxetane groups include bisphenol A type epoxy resin, bisphenol A type oxetane resin, bisphenol F type epoxy resin, bisphenol F type oxetane resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, epoxy-containing silicones such as polymethyl (glycidoxypropyl) siloxane, etc., however, the compound is not limited thereto. Specifically, EPICLON (registered trademark) 850-S, EPICLON HP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON EXA-4710, EPICLON HP-4770, EPICLON EXA-859CRP, EPICLON EXA-1514, EPICLONEXA-4880, EPICLON EXA-4850-150, EPICLON EXA-4850-1000, EPICLON EXA-4816 and EPICLONEXA-4822 (in the above, trade names, manufactured by Dainippon Ink & Chemicals, Inc.), RIKARESIN (registered trademark) BEO-60E (trade name, manufactured by New Japan Chemical) which are commercially available from various companies may be included. Co., Ltd.), EP-4003S and EP-4000S (trade name, manufactured by ADEKA Corporation), etc. Two or more types thereof may be included.

[0162] As the crosslinking agent, 2-[[4-[2-[4-[1,1-bis[4-(oxiran-2-ylmethoxy)phenyl]ethyl]phenyl]prop-2-yl]phenoxy]methyl]ethylene oxide, tetraethylene glycol dimethacrylate, or the like can be used.

[0163] The content of the crosslinking agent is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, even more preferably 10 parts by weight or more, relative to 100 parts by weight of the polyimide, and from the viewpoint of maintaining mechanical properties such as elongation, it is preferably 300 parts by weight or less, more preferably 200 parts by weight or less.

[0164] In one embodiment of the present disclosure, in order to improve the resolution of the concavo-convex pattern, the photosensitive resin composition may further include a monomer having a photopolymerizable unsaturated bond.

[0165] As such a monomer, a (meth)acrylic compound which undergoes a radical polymerization reaction by a photopolymerization initiator is preferred, and, although not particularly limited to the following, examples thereof may include: monoacrylate or diacrylate and monomethacrylate or dimethacrylate of ethylene glycol or polyethylene glycol (including diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate); monoacrylate or diacrylate and monomethacrylate or dimethacrylate of propylene glycol or polypropylene glycol; monoacrylate, diacrylate or triacrylate and monomethacrylate, dimethacrylate or trimethacrylate of glycerol; cyclohexane diacrylate and cyclohexane dimethacrylate; diacrylate and dimethacrylate of 1,4-butanediol; 1,6- Diacrylates and dimethacrylates of hexanediol; diacrylates and dimethacrylates of neopentyl glycol; monoacrylates or diacrylates and monomethacrylates or dimethacrylates of bisphenol A; benzyltrimethacrylate; isobornyl acrylate and isobornyl methacrylate; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane triacrylate and trimethylolpropane trimethacrylate; diacrylates or triacrylates and dimethacrylates or trimethacrylates of glycerol; diacrylates, triacrylates or tetraacrylates and dimethacrylates, trimethacrylates or tetramethacrylates of pentaerythritol; and compounds such as ethylene oxide adducts or propylene oxide adducts of these compounds.

[0166] The content of the monomer having a photopolymerizable unsaturated bond is preferably 1 part by weight to 50 parts by weight relative to 100 parts by weight of the polyimide.

[0167] The antioxidant can improve the elongation characteristics of the cured film after reliability evaluation or the adhesion to the metal material. In addition, the antioxidant can inhibit the oxidative degradation of the aliphatic group or phenolic hydroxyl group of the polyimide resin, and can inhibit metal oxidation by the rust-proof effect on the metal material. Specific examples of the antioxidant may include the following compounds, etc., but are not limited thereto.

[0168]

[0169]

[0170]

[0171]

[0172] The content of the antioxidant is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the polyimide. When the content of the antioxidant is less than 0.1 parts by weight, it is difficult to obtain the effect of improving the elongation characteristics after reliability or the adhesion to the metal material, and when the content is more than 10 parts by weight, there is a problem of reducing the sensitivity of the photosensitive resin composition due to the interaction with the photosensitizer.

[0173] The surfactant is a silicone-based surfactant or a fluorine-based surfactant, and specifically, as the silicone-based surfactant, BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-336 manufactured by BYK-Chemie GmbH can be used. BYK-344, BYK-345v346, BYK-348, BYK-354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380 and BYK-390, etc., and as fluorine-based surfactants, DIC (DaiNippon Ink & Chemicals, Inc.) F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484 , F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF, TF-1131, TF1132, TF1027SF, TF-1441 and TF-1442, etc., however, the surfactant is not limited to this.

[0174] As the solvent, a compound capable of forming a photosensitive resin composition known in the art may be used without particular limitation. Non-limiting examples of the solvent may include one or more types of compounds selected from esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

[0175] The ester-based solvent may include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl oxyacetates (examples: methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropanoates (examples: methyl 3-oxypropanoate, ethyl 3-oxypropanoate, etc. (e.g., methyl 3-methoxypropanoate, ethyl 3-methoxypropanoate, ethyl 3-methoxypropanoate, etc.) ethoxypropionic acid methyl ester, ethyl 3-ethoxypropionic acid ester, etc.)), alkyl 2-oxypropionic acid esters (examples: methyl 2-oxypropionic acid methyl ester, ethyl 2-oxypropionic acid ester, propyl 2-oxypropionic acid ester, etc. (for example, methyl 2-methoxypropionic acid methyl ester, ethyl 2-methoxypropionic acid ester, propyl 2-methoxypropionic acid ester, methyl 2-ethoxypropionic acid ester, ethyl 2-ethoxypropionic acid ester)), methyl 2-oxy-2-methylpropionic acid ester and ethyl 2-oxy-2-methylpropionic acid ester (for example, methyl 2-methoxy-2-methylpropionic acid methyl ester, ethyl 2-ethoxy-2-methylpropionic acid ester, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.

[0176] The ether-based solvent may include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.

[0177] The ketone-based solvent may include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like.

[0178] The aromatic hydrocarbon-based solvent may include toluene, xylene, anisole, limonene, and the like.

[0179] The sulfoxide-based solvent may include dimethyl sulfoxide and the like.

[0180] [Insulating film]

[0181] Furthermore, another embodiment of the present application provides an insulating film including the photosensitive resin composition or a cured product thereof.

[0182] The insulating film may include the photosensitive resin composition as it is.

[0183] The insulating film may include a cured product of the photosensitive resin composition.

[0184] Examples of a light source for curing the photosensitive resin composition according to one embodiment of the present disclosure may include a mercury vapor arc, a carbon arc, a Xe arc, etc., which emit light having a wavelength of 250 nm to 450 nm, but are not limited thereto.

[0185] After curing the photosensitive resin composition, the insulating film may be further subjected to heat treatment as needed.

[0186] The heat treatment may be performed using a heating device such as a hot plate, a hot air circulation furnace, an infrared furnace, etc., and may be performed at a temperature of 180°C to 250°C or 190°C to 220°C.

[0187] The insulating film exhibits excellent chemical resistance and mechanical characteristics and can be preferably used as an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, etc. In addition, the insulation can be applied to a photoresist, a resist, a top solder resist, etc.

[0188] The insulating film may include a support or a substrate.

[0189] The support or substrate is not particularly limited, and those known in the art can be used. For example, it can include a substrate for electronic components or those on which a predetermined wiring pattern is formed. Examples of substrates can include substrates made of metals such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, aluminum, gold and nickel, glass substrates, etc. Examples of materials for wiring patterns can include copper, solder, chromium, aluminum, nickel, gold, etc., but are not limited thereto. The support or substrate can preferably be a silicon wafer.

[0190] The coating method is not particularly limited, however, spraying, roll coating, spin coating, etc. may be used, and generally, spin coating is widely used. In addition, after the coating film is formed, some residual solvent may be removed under reduced pressure in some cases.

[0191] In one embodiment of the present disclosure, the thickness of the insulating film may be 1 μm to 100 μm. When the thickness of the insulating film satisfies the above range, an insulating film with excellent chemical resistance and mechanical properties targeted by the present application may be obtained. The thickness of the insulating film may be measured using a scanning electron microscope (SEM).

[0192] An embodiment of the present disclosure provides a semiconductor device including the insulating film.

[0193] A semiconductor device may be manufactured by further including various components generally used in the art in addition to the insulating film.

[0194] Embodiments of the invention

[0195] Hereinafter, the present disclosure will be described in detail with reference to the embodiments to specifically describe the present disclosure. However, the embodiments according to the present disclosure can be modified into various different forms, and the scope of the present disclosure should not be interpreted as being limited to the embodiments described below. The embodiments of this specification are provided to more fully describe the present disclosure to those of ordinary skill in the art.

[0196] Synthesis Examples 1 to 10 (Polyimide Resins A to J) and Comparative Synthesis Examples 1 to 7 (Polyimide Resins K to Q)

[0197] Into a 1,000mL round-bottom flask as a reaction vessel, a diamine monomer not containing a flexible functional group, a diamine monomer containing a flexible functional group and 300g of PGMEA (propylene glycol methyl ether acetate) solvent were sequentially introduced, and after the temperature was raised to 120°C and the mixture was completely dissolved by stirring, the flask was cooled to 80°C. Aromatic dianhydride monomer, aliphatic dianhydride monomer, end-capping monomer and 30g of toluene were introduced together, and the resultant was stirred at 150°C. After the reaction mixture was completely dissolved, the flask was cooled to 50°C, and 3mmol of r-VL (gamma valerolactone, γ-valerolactone) and 7mmol of triethylamine (TEA) diluted in 10g of propylene glycol monomethyl acetate (PGMEA) were then introduced therein. A Dean-Stark distillation apparatus was installed on the reaction vessel to remove water therethrough, and the mixture was then stirred at 175°C for 18 hours. After removing the toluene introduced into the mixture solution, the solution was cooled to room temperature to collect the polymer. The weight average molecular weight (Mw) of the collected polymer was determined using gel permeation chromatography (GPC).

[0198] The types of monomers used to synthesize the polyimide resins A to Q, the molar numbers (mmol) of the introduced monomers, the weight average molecular weight and the polydispersity index (PDI) of the collected polymers are shown in Table 1 below.

[0199] [Table 1]

[0200]

[0201] The abbreviations of the diamine monomers and dianhydride monomers shown in Table 1 and the detailed names of the products are as follows.

[0202] As diamine monomers not including a flexible functional group, Bis-APAF is 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, BAPP is 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4′-ODA is 4,4′-oxydiphenylamine, HAB is 3,3′-dihydroxy-4,4′-diaminobiphenyl, and p-PDA is p-phenylenediamine.

[0203] As diamine monomers containing flexible functional groups, ED-2003, ED-900, ED-600 and D400 are Products, EC130 and EC280 are products, and DAD is dodecane-1,12-diamine.

[0204] As the aromatic dianhydride monomer, ODPA is 4,4′-oxydiphthalic anhydride, 6FDA is 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, PMDA is pyromellitic dianhydride, and BPDA is 3,3′,4,4′-biphenyltetracarboxylic dianhydride.

[0205] As the aliphatic dianhydride monomer, CBDA is cyclobutane-1,2,3,4-tetracarboxylic dianhydride, H-PMDA is 1,2,4,5-cyclohexanetetracarboxylic dianhydride, H-BPDA is dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, and BT-100 is 1,2,3,4-butane-tetracarboxylic dianhydride.

[0206] As the end-capping compound, TMA is trimellitic anhydride, 3AP is 3-aminophenol, PA is phthalic anhydride, and NDA is cis-5-norbornene-endo-2,3-dicarboxylic anhydride.

[0207] Photosensitive resin composition

[0208] Each polyimide resin of the previously prepared Synthesis Examples and Comparative Synthesis Examples, a curing agent, a photoactive compound, a surfactant, and a solvent were mixed in the composition and content described below, and then stirred for 24 hours to prepare a positive photosensitive resin composition.

[0209] Example 1. Photosensitive resin composition A

[0210] 23.8% of the polyimide resin A of Synthesis Example 1, 5.00% of EXA-4850-1000 (DIC) as a bisphenol A type epoxy resin, 1.45% of YDF-170 (Kukdo Chemical Co., Ltd.) as a bisphenol F type epoxy resin, 0.70% of HMMM (hexamethoxymethylmelamine, TCI) as a methylol curing agent, 3.60% of TPD523 (Miwon Commercial Co., Ltd.) as a photosensitive material, 0.05% of R-40 (DIC) as a surfactant, 50.40% of PGMEA and 15.00% of GBL (γ-butyrolactone) were mixed and then stirred for 24 hours to prepare a positive photosensitive resin composition. Each value represents the weight % of each component based on 100 weight % of the entire resin composition.

[0211] Examples 2 to 10 and Comparative Examples 1 to 7

[0212] In Examples 2 to 10, photosensitive resin compositions were prepared in the same manner as in Example 1, except that polyimide resins B to J were used instead of polyimide resin A. In Comparative Examples 1 to 7, photosensitive resin compositions were prepared in the same manner as in Example 1, except that polyimide resins K to Q were used instead of polyimide resin A.

[0213] <Experimental example>

[0214] 1) Preparation of samples for measurement

[0215] The photosensitive resin composition prepared above was spin-coated on a 6-inch wafer to form a film, and the solvent was evaporated, and the film was initially cured for 2 minutes at 120°C. The film was finally cured for 2 hours at 180°C in an oven (INH oven manufactured by Koyo) under a nitrogen atmosphere, and the thickness of the film after final curing was 10 μm. In order to remove the cured film from the wafer, the film was immersed in 2.5% HF diluted in DI water (deionized water) for 30 minutes, and when the film floated, the film was taken out and washed three times with DI water. The cured film obtained was dried in a convection oven at 40°C for 1 hour, and then cut into a size of 10 cm × 1 cm to prepare a sample for tensile measurement.

[0216] 2) Measurement of Young's modulus, tensile strength and elongation

[0217] The prepared sample was loaded into UTM (Universal Testing Machine, manufactured by ZwickRoell) at a temperature of 25° C., and then Young's modulus, tensile strength and elongation were measured. Here, the measuring length of the sample was set to 5 cm, and the tensile speed was set to 10.0 mm / min.

[0218] 3) Glass transition temperature (T g ) and the coefficient of thermal expansion (CTE)

[0219] The sample prepared above was heated from a temperature of 25° C. at a rate of 10° C. / min in a nitrogen atmosphere using a Q400 apparatus manufactured by TA Instruments to measure a glass transition temperature and a thermal expansion coefficient.

[0220] 4) Optimal exposure dose (E op )

[0221] The photosensitive resin composition prepared above was spin-coated on a 6-inch wafer, and then soft-baked (pre-baked, SOB) at 120° C. for 2 minutes, and then exposed using an exposure machine at intervals of 10 mJ from 200 mJ / cm 2 Up to 500mJ / cm 2 After developing in a 2.38% TMAH (tetramethylammonium hydroxide) aqueous solution at 23° C. for 120 seconds, a resist pattern was prepared, and then E was determined using a SEM (scanning electron microscope). op .

[0222] [Table 2]

[0223]

[0224] It can be seen that Examples 1 to 10, which are photosensitive resin compositions according to the present disclosure in which the -F / -OH ratio contained in the polyimide repeating unit satisfies a ratio greater than or equal to 2 and less than or equal to 5, have the advantages of being easily soluble in PGMEA (an environmentally friendly aqueous solvent) and being developable with TMAH (an aqueous developing solution), and at the same time, also have excellent elongation and excellent glass transition temperature. On the other hand, it can be seen that in Comparative Example 2 in which the -F / -OH ratio is 33, the composition cannot be developed with TMAH (an aqueous developing solution), and in Comparative Examples 1 to 5 in which the -F / -OH ratio is greater than 5, the elongation and glass transition temperature characteristics are poor compared to the examples. In Comparative Examples 6 and 7 in which the -F / -OH ratio is less than 2, the Elongation and Glass Transition Temperature characteristics are poor compared to the examples. op increases, and therefore, the exposure energy required for pattern formation increases.

[0225] 5) Measurement of dielectric constant

[0226] The dielectric constant was measured using a PNA-L network analyzer N5230A (Agilent Technologies) and a split dielectric resonator (QWED) device. Specifically, a sample in a film state with a size of 5 cm×5 cm or more was prepared. 10 GHz was set in the PNA-L network analyzer N5230A. A blank state was checked in the split dielectric resonator. In the blank state, the resonant frequency and Q value were measured. The sample was introduced into the SPD, and after the thickness value was entered, the resonant frequency and Q value were measured. Thus, the Dk / Df value was calculated.

[0227] 6) Measurement of chemical resistance

[0228] Prepare a sample coated on a wafer. Measure the thickness before the chemical resistance evaluation. Heat the RDL stripper solution on a 70°C hot plate. Immerse the sample in the RDL stripper solution and leave it there for 1 minute. At the end of the time, wash the sample under running water. Measure the thickness after the chemical resistance evaluation. After the measurement, calculate the change in thickness before and after the chemical resistance evaluation as %.

[0229] 5% or less: ○, 5% to 10%: △, 10% or more: X

[0230] [Table 3]

[0231] Dk Df Chemical resistance Example 1 3.1999 0.0204 ○ Example 2 3.1907 0.0228 ○ Example 3 3.1850 0.0225 ○ Example 4 3.1966 0.0240 ○ Example 5 3.2105 0.0244 ○ Example 6 3.1919 0.0237 ○ Example 7 3.2060 0.0255 ○ Example 8 3.1949 0.0250 ○ Example 9 3.2080 0.0257 ○ Example 10 3.1990 0.0252 O Comparative Example 1 3.1856 0.0267 Δ Comparative Example 2 3.1531 0.0192 X Comparative Example 3 3.2005 0.0260 Δ Comparative Example 4 3.2019 0.0301 ○ Comparative Example 5 3.1994 0.0299 ○ Comparative Example 6 3.2009 0.0262 Δ Comparative Example 7 3.1956 0.0259 X

[0232] In Examples 1 to 10 of the photosensitive resin composition according to the present disclosure, in which the ratio of -F / -OH contained in the polyimide repeating unit satisfies 2 or more and 5 or less, the dielectric constant (Dk) and the dielectric loss (D f ) is low and has excellent chemical resistance.

[0233] On the other hand, Comparative Examples 1 to 5, in which the -F / -OH ratio was greater than 5, had poor chemical resistance characteristics and high dielectric loss (D f ), and showed poor performance as an insulating film compared with Examples 1 to 10. In particular, in Comparative Example 2 where the -F / -OH ratio was 33, the chemical resistance was evaluated to be very poor. In addition, in Comparative Examples 6 and 7 where the -F / -OH ratio was less than 2, the chemical resistance characteristics were poor, and the dielectric loss (Df) was also somewhat high.

[0234] Therefore, since the polyimide repeating unit includes -F and -OH functional groups, and the -F / -OH ratio contained in the repeating unit satisfies 2≤-F / -OH≤5, the photosensitive resin composition according to one embodiment of the present disclosure has the advantages of being easily soluble in PGMEA (an environmentally friendly aqueous solvent) and being developable with TMAH (an aqueous developing solution), and at the same time, has excellent characteristics such as dielectric loss (Df ) and elongation, and also has excellent chemical resistance.

[0235] In the above, the present disclosure is described using limited embodiments, however, the present disclosure is not limited thereto, and it is obvious that various changes and modifications can be made by those skilled in the art within the technical concept of the present disclosure and the scope of equivalents of the described claims.

Claims

1. A photosensitive resin composition comprising a polyimide containing a repeating unit represented by the following Chemical Formula 1 to Chemical Formula 4, The ratio of the total number of -F functional groups to the total number of -OH functional groups contained in the repeating units represented by Chemical Formulae 1 to 4 satisfies 2≤-F / -OH≤5: [Chemical formula 1] [Chemical formula 2] [Chemical formula 3] [Chemical formula 4] In Chemical Formulae 1 to 4, A1 is a tetravalent aliphatic organic group; A2 is a tetravalent aromatic ring group; B1 is a divalent aromatic ring group; B2 is a flexible functional group; p1 to p4 are each independently an integer from 1 to 10,000; and At least one of A1, A2, B1, and B2 includes a -F functional group, a -OH functional group, or a -F functional group and a -OH functional group. 2 . The photosensitive resin composition according to claim 1 , wherein a ratio of the total number of repeating units represented by Chemical Formula 1 and Chemical Formula 3 to the total number of repeating units represented by Chemical Formula 2 and Chemical Formula 4 is 0.01 to 1.

0. 3 . The photosensitive resin composition of claim 1 , wherein a ratio of the total number of repeating units represented by Chemical Formula 1 and Chemical Formula 3 to the total number of repeating units represented by Chemical Formula 1 to Chemical Formula 4 is 0.05 to 0.

5. 4 . The photosensitive resin composition of claim 1 , wherein a ratio of the total number of repeating units represented by Chemical Formula 3 and Chemical Formula 4 to the total number of repeating units represented by Chemical Formula 1 to Chemical Formula 4 is 0.05 to 0.

5.

5. The photosensitive resin composition according to claim 1, wherein the tetravalent aliphatic organic group comprises one or more types selected from the group consisting of a substituted or unsubstituted tetravalent aliphatic cyclic group, the following Chemical Formula 5, and the following Chemical Formula 6: [Chemical formula 5] [Chemical formula 6] Wherein in Chemical Formula 5 and Chemical Formula 6, L1 is a direct bond; a substituted or unsubstituted alkylene group; -O-; -SO2-; -CO-; or -OCO-; R1 to R6 are the same as or different from each other and are each independently hydrogen; substituted or unsubstituted alkyl; or carboxyl; m and n are 2; R5 are the same as or different from each other; and R6 are the same as or different from each other.

6. The photosensitive resin composition according to claim 1, wherein the tetravalent aliphatic organic group comprises one or more types selected from the following chemical formulas:

7. The photosensitive resin composition according to claim 1, wherein the tetravalent aromatic ring group comprises one or more types selected from the group consisting of a substituted or unsubstituted tetravalent aromatic monocyclic ring and the following Chemical Formula 7: [Chemical formula 7] Wherein in Chemical Formula 7, L2 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO2-; -CO-; or -OCO-; R1 and R2 are the same as or different from each other and are each independently hydrogen; substituted or unsubstituted alkyl; or carboxyl; m and n are the same as or different from each other and are each independently an integer from 0 to 3; When m is 2 or more, R1 are the same as or different from each other; and When n is 2 or more, R2's are the same as or different from each other.

8. The photosensitive resin composition according to claim 1, wherein the divalent aromatic ring group comprises one or more types selected from the group consisting of a substituted or unsubstituted divalent aromatic monocyclic ring, the following Chemical Formula 8, and the following Chemical Formula 9: [Chemical formula 8] [Chemical formula 9] Wherein in Chemical Formula 8 and Chemical Formula 9, L3 and L4 are the same as or different from each other and are each independently a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO2-; -CO-; or -OCO-; R1 to R4 are the same as or different from each other and are each independently hydrogen; substituted or unsubstituted alkyl; substituted or unsubstituted alkoxy; hydroxy; or substituted or unsubstituted amino; m1, m2, n1 and n2 are the same as or different from each other and are each independently an integer from 0 to 4; When m1 is 2 or more, R1 are the same as or different from each other; When n1 is 2 or more, R2 are the same as or different from each other; When m2 is 2 or more, R3 are the same as or different from each other; and When n2 is 2 or more, R4 are the same as or different from each other.

9. The photosensitive resin composition according to claim 1, wherein the flexible functional group comprises one or more types selected from the following Chemical Formulas 10 to 13: [Chemical formula 10] [Chemical formula 11] [Chemical formula 12] [Chemical formula 13] In Chemical Formulas 10 to 13, X1 to X3 are the same as or different from each other, and are each independently -O-; or -CH2-; La1 to La11 are the same as or different from each other, and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group; R1 to R6 are the same as or different from each other and are each independently hydrogen; or a substituted or unsubstituted alkyl group; x, y, and z are each independently a real number ranging from 0 to 50; and a1 is a real number ranging from 1 to 30.

10. The photosensitive resin composition according to claim 1, wherein the flexible functional group comprises one or more types selected from the following chemical formulas: Wherein in the chemical formula, Each n is independently a real number from 1 to 30; and x, y and z are each independently a real number of 1 to 50. 11 . The photosensitive resin composition according to claim 1 , further comprising one or more types selected from the group consisting of a photosensitizer, a crosslinking agent, an antioxidant, a surfactant, and a solvent. 12 . An insulating film comprising the photosensitive resin composition according to claim 1 or a cured product thereof. 13 . A semiconductor device comprising the insulating film according to claim 12 .

Images