CN115536841A - Negative photosensitive resin and preparation method and application thereof - Google Patents
Negative photosensitive resin and preparation method and application thereof Download PDFInfo
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- CN115536841A CN115536841A CN202211301073.5A CN202211301073A CN115536841A CN 115536841 A CN115536841 A CN 115536841A CN 202211301073 A CN202211301073 A CN 202211301073A CN 115536841 A CN115536841 A CN 115536841A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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Abstract
The invention provides a negative photosensitive resin and a preparation method and application thereof, wherein the negative photosensitive resin is shown as a formula (1), wherein, -OR 1 Each occurrence is independently selected from a first group and a second group, the first group is an esterified residue of a hydroxyl-containing acrylate monomer, and the second group comprises at least one of an esterified residue of a hydroxyl-containing polyol ether monomer and an esterified residue of a hydroxyl-containing polyol ester monomer; and at least partially-OR 1 Selected from the second group;
each occurrence is independently selected from aromatic tetracarboxylic acid monomer residues with 6-60 ring atoms,
each occurrence is independently selected from aromatic diamine monomer residues with 6-60 ring atoms; x 1 Each occurrence is independently selected from H or alkyl with 1-10 carbon atoms, b is selected from any integer of 1-4, and Y is selected from single bond, O or alkane subunit with 1-10 carbon atoms; m satisfies: 0 < m.ltoreq.1, n represents the degree of polymerization, and x represents the linking site.
Description
Technical Field
The invention relates to the field of functional polymer materials, in particular to a negative photosensitive resin and a preparation method and application thereof.
Background
In recent years, ultra large scale integrated circuit (ULIC) fabrication and packaging technologies have been developed to integrate and integrate with each other. In order to realize high-density, ultra-thin and ultra-micro packaging of the ULIC circuit, many integrated circuit manufacturers need to continue to manufacture multiple layers of metal interconnection circuits on the surface of the ulisi circuit after completing the manufacture of the ulisi circuit, so as to realize advanced IC packaging such as BGA, CSP, WLP, siP, and the like. The ultraviolet photoetching technology is usually adopted to alternately stack the photosensitive resin interlayer dielectric insulating layers and the metal copper conductor wiring layers.
Photosensitive polyimide resins (PSPI) are important insulating materials in the semiconductor industry due to their excellent thermal stability, mechanical strength, dielectric properties and solution processability, and are often used as buffer layers, passivation layers, planarization layers for multi-layer interconnects, interlayer dielectric layers and the like in integrated circuits. The photosensitive polyimide-based resin is classified into a positive type, in which the exposed region is dissolved in a developer, and a negative type, in which the exposed region is crosslinked and cured and is not dissolved in the developer. The negative photosensitive polyimide is crosslinked to form a crosslinked network structure through photosensitive groups under the ultraviolet irradiation of an exposure area, so that negative photoetching is realized.
However, the conventional negative photosensitive polyimide has the problems of difficulty in combining high resolution and high elongation at break, difficulty in meeting the application requirements of the polyimide as a dielectric layer material for packaging, and incapability of meeting the requirements of an integrated circuit on durability and impact resistance. Thus, the prior art remains to be improved.
Disclosure of Invention
Based on the above, the invention provides a negative photosensitive resin, and a preparation method and an application thereof, wherein the negative photosensitive resin has high resolution and flexibility, and further improves high durability and impact resistance.
The technical scheme of the invention is as follows.
One aspect of the present invention provides a negative photosensitive resin, which is represented by formula (1):
wherein, -OR 1 Each occurrence is independently selected from a first group which is an esterified residue of a hydroxyl-containing acrylate monomer and a second group which comprises at least one of an esterified residue of a hydroxyl-containing polyol ether monomer and an esterified residue of a hydroxyl-containing polyol ester monomer; and at least partially-OR 1 Selected from the second group;
X 1 each occurrence is independently selected from H or alkyl with 1-10 carbon atoms, b is selected from any integer of 1-4, and Y is selected from single bond, O or alkane subunit with 1-10 carbon atoms;
m satisfies: 0 < m.ltoreq.1, n represents the degree of polymerization, and x represents the linking site.
In some embodiments, the negative photosensitive resin has a molar ratio of the first group to the second group of 1 (0.01 to 0.4).
In some of these embodiments, ar 1 Each occurrence is independently selected from any of the following structures:
wherein R is 3 Each occurrence is independently selected from C1-5 alkane subunit or O;
* Indicates the attachment site.
In some of these embodiments, ar 1 Each occurrence is independently selected from any of the following structures:
* Indicates the attachment site.
In some of these embodiments, the hydroxyl-containing polyol ether-based monomer includes at least one of the following structures:
wherein R is 4 Selected from alkyl with 1 to 6 carbon atoms or aryl with 6 to 10 ring atoms, n 1 Is any integer of 1 to 4; and/or
The hydroxyl-containing polyol ester monomer has the following structure:
wherein R is 5 Is selected from alkyl with 1 to 6 carbon atoms or aryl with 6 to 10 ring atoms, and m is any integer of 1 to 4.
In some embodiments, the hydroxyl group-containing polyol ether-based monomer includes at least one of the following structures:
wherein n is 1 Is any integer of 1 to 4; and/or
The hydroxyl-containing polyol ester monomer comprises at least one of the following structures:
wherein m is any integer of 1 to 4.
In some of these embodiments, the hydroxyl-containing acrylate monomer comprises at least one of the following structures:
wherein n is 2 Is any integer of 1 to 4.
In some of these embodiments, ar 2 Each occurrence is independently selected from any of the following structures:
* Indicates the attachment site.
In some embodiments, m is more than or equal to 0.1 and less than or equal to 1, n is any integer from 10 to 100; and/or
X 1 Each occurrence is independently selected from H or alkanyl with 1-5 carbon atoms; and/or
Y is selected from a single bond or O.
In another aspect of the present invention, there is provided a method for preparing the above negative photosensitive resin, comprising the steps of:
carrying out esterification reaction on dianhydride compounds formed by at least part of the first monomer and/or the second monomer and the aromatic tetracid monomer with the ring atom number of 6-60 to prepare a precursor;
wherein the first monomer is the hydroxyl-containing acrylate monomer, and the second monomer comprises at least one of the hydroxyl-containing polyol ether monomer and the hydroxyl-containing polyol ester monomer;
performing polycondensation on the rest of the first monomer and/or the second monomer, the precursor, the third monomer shown in the formula (2) and the aromatic diamine monomer with the ring atom number of 6-60 to prepare the negative photosensitive resin shown in the formula (1);
in still another aspect of the present invention, there is provided a photoresist, the composition of which comprises the negative photosensitive resin as described above.
In another aspect of the present invention, a method of negative tone development is provided, comprising the steps of:
coating the photoresist on a substrate, prebaking, photoetching, exposing and developing, dissolving the photoresist in a non-exposure area, and crosslinking and curing the photoresist in an exposure area to form a cured resin to form a pattern layer.
In still another aspect of the present invention, there is provided a cured resin obtained from a raw material comprising the photoresist as described above, or
The cured resin was prepared using the negative tone development method described above.
The negative photosensitive resin has a specific structure, a side chain of the negative photosensitive resin contains a specific first group and a specific second group, the first group is an esterified residue of a hydroxyl-containing acrylate monomer and is used as a photosensitive group, photosensitivity is given to the resin, and photocrosslinking is realized; the second group comprises at least one of esterified residue of hydroxyl-containing polyol ether monomer and esterified residue of hydroxyl-containing polyol ester monomer, on one hand, the second group can dilute the photosensitive group and adjust the crosslinking degree of the negative photosensitive resin to avoid reduction of mechanical properties caused by excessive crosslinking, and on the other hand, the second group with a specific structure can weaken attraction among polymer molecular chains, increase the distance among the polymer molecular chains, reduce entanglement among the polymer molecular chains and further improve the flexibility of the polymer molecular chains, so that the flexibility of the polymer molecular chains is improved while excellent high resolution is maintained.
Drawings
FIG. 1 is an optical microscope photograph of a developed pattern obtained in example 1;
FIG. 2 is an optical microscope photograph of a developed pattern obtained in example 2;
FIG. 3 is an optical microscope photograph of a developed pattern obtained in comparative example 1;
fig. 4 is an optical microscope photograph of the developed pattern obtained in comparative example 2.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the present invention, when the same substituent is present in plural times, it may be independently selected from different groups. Such as formula (1) containing a plurality of-OR 1 Then is-OR 1 Can be independently selected from different groups.
In the present invention, "-" indicates a connection site.
In the present invention, when the attachment site is not specified in the group, it means that an optional attachment site in the group is used as the attachment site.
In the context of the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached at an optional position on the ring, for example
Wherein R is connected with any substitutable site of the benzene ring; when in useWhen a single bond having two substituents is extended through the ring, it is stated that the two substituents may be attached to the ring at optional positions, and the attachment positions of the two substituents are different. For example
In (3), since there is only one hydrogen atom on both unsubstituted carbon atoms on the phenyl ring, two substituents are not attached to the same carbon atom on the same phenyl ring, in other words, the two substituents are not attached to the ring at the same site. Further, when R is H, this represents that the hydrogen on the benzene ring is not substituted by other substituents.
In the present invention, when two groups are linked by a point of attachment, e.g.
Wherein R is selected from a single bond, meaning that the two groups need not be linked by a particular group, but are directly linked by a single bond, i.e. R is selected from a single bond
"alkanyl" as used herein refers to a group formed upon loss of one hydrogen from an alkane, for example, methane is lost one hydrogen to form a methyl group; "Alkylidene or alkylene" refers to a group formed from an alkane that has lost two hydrogens, for example methane has lost two hydrogens to form a methylene group.
The skilled person in the present application has found in many years of research and production in the field of photosensitive resins: to achieve high resolution of the lithographic pattern, it is generally necessary to introduce highly reactive photosensitive groups or to increase the content of photosensitive groups to increase sensitivity, but increasing the content of photosensitive groups may cause excessive crosslinking of the photosensitive resin during exposure, adversely affect resolution, and greatly reduce flexibility.
Based on this, the technical solution of the present application is obtained after a lot of creative experimental researches.
The embodiment of the invention provides a negative photosensitive resin, which is shown as a formula (1):
wherein, -OR 1 Each occurrence is independently selected from a first group and a second group, wherein the first group is an esterified residue of a hydroxyl-containing acrylate monomer, and the second group comprises at least one of an esterified residue of a hydroxyl-containing polyol ether monomer and an esterified residue of a hydroxyl-containing polyol ester monomer; and at least partially-OR 1 Selected from the second group;
X 1 each occurrence is independently selected from H or alkyl with 1-10 carbon atoms, b is selected from any integer of 1-4, and Y is selected from single bond, O or alkane subunit with 1-10 carbon atoms;
m satisfies: 0 < m.ltoreq.1, n represents the degree of polymerization, and x represents the linking site.
The negative photosensitive resin has a specific structure, wherein a side chain contains a specific first group and a second group, the first group is an esterified residue of a hydroxyl-containing acrylate monomer and is used as a photosensitive group to endow the resin with photosensitivity and realize photocrosslinking, the second group comprises at least one of an esterified residue of a hydroxyl-containing polyol ether monomer and an esterified residue of a hydroxyl-containing polyol ester monomer, on one hand, the second group can dilute the photosensitive group and adjust the crosslinking degree of the negative photosensitive resin to avoid reduction of mechanical properties caused by excessive crosslinking, and on the other hand, the second group with the specific structure can weaken attraction among polymer molecular chains, increase the distance among the polymer molecular chains, reduce entanglement among the polymer molecular chains and further improve the flexibility of the polymer molecular chains, so that the flexibility of the negative photosensitive resin is improved while excellent high resolution is maintained.
It is understood that the esterified residue of the hydroxyl group-containing acrylic monomer refers to a group remaining in the formed ester compound when the hydroxyl group in the hydroxyl group-containing acrylic monomer is esterified with a carboxylic acid, for example
The esterified residues of (a) are:
wherein denotes a site of attachment to a carboxylic acid group moiety in the formed ester compound.
Similarly, the esterified residue of the hydroxyl group-containing polyol ether monomer and the esterified residue of the hydroxyl group-containing polyol ester monomer are similar in definition to the esterified residue of the hydroxyl group-containing acrylate monomer.
In some of these embodiments, the molar ratio of the first group to the second group is 1 (0.01 to 0.4).
The resolution and flexibility of the negative photosensitive resin are further improved by adjusting the proportion of the second group.
It should be noted that when a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as ranges defined for each and every value between such minimum and maximum values.
For example "(0.01-0.4): 1" includes but is not limited to: 0.01.
In some of these embodiments, ar 1 Each occurrence is independently selected from any of the following structures:
wherein R is 3 Each occurrence is independently selected from the group consisting of 1 to 5 carbon atomsOr O;
* Indicates the attachment site.
In some of these embodiments, R 3 Each occurrence is independently selected from methylene, ethylene, isopropylidene or O.
In some of these embodiments, ar 1 Each occurrence is independently selected from any of the following structures:
* Indicates the attachment site.
In some of these embodiments, ar 1 Each occurrence is independently selected from any of the following structures:
in some of these embodiments, ar 1 Each occurrence is independently selected from any of the following structures:
in some of these embodiments, ar 2 Each occurrence is independently selected from any of the following structures:
* Indicates the attachment site.
In some of these embodiments, ar 2 Each occurrence is independently selected from any of the following structures:
* Indicates the attachment site.
In some of these embodiments, ar 2 Each occurrence is independently selected from any of the following structures:
in some of these embodiments, the hydroxyl-containing polyol ether-based monomer includes at least one of the following structures:
wherein R is 4 Selected from alkyl with 1 to 6 carbon atoms or aryl with 6 to 10 ring atoms, n 1 Is any integer of 1 to 4.
In some of these embodiments, R 4 Selected from straight chain or branched chain alkyl or phenyl with 1 to 6 carbon atoms.
In some of these embodiments, the hydroxyl-containing polyol ether-based monomer comprises at least one of the following structures:
wherein n is 1 Is any integer of 1 to 4.
Understandably, n 1 Each occurrence is independently selected from any integer of 1,2, 3 or 4.
In some of these embodiments, n 1 Is any integer of 1 to 4.
In a specific example, the hydroxyl-containing polyol ether monomer is ethylene glycol monomethyl ether, and has the following structure:
in some of these embodiments, the hydroxyl-containing polyol ester monomers have the following structure:
wherein R is 5 Is selected from alkyl with 1 to 6 carbon atoms or aryl with 6 to 10 ring atoms, and m is any integer of 1 to 4.
In some of these embodiments, R 5 Is selected from C1-6 branched chain or C1-6 straight chain alkyl or phenyl.
In some of these embodiments, R 5 Selected from methyl or phenyl.
In some of these embodiments, the hydroxyl-containing polyol ester monomers include at least one of the following structures:
in some of these embodiments, m is selected from any integer of 1,2, 3, 4.
In some embodiments, m is an integer from 1 to 2.
The hydroxyl group-containing acrylic ester monomer includes at least one of esters of hydroxyl group-containing acrylic acid and its homologues.
In some of these embodiments, the hydroxyl-containing acrylate monomer comprises at least one of the following structures:
wherein n is 2 Is any integer of 1 to 4.
Understandably, n 2 Is any integer of 1,2, 3 or 4.
In some of whichIn the examples, n 2 Is an integer of 1 to 2.
In a specific example, the hydroxyl-containing acrylate monomer is hydroxyethyl methacrylate, and has the following structure:
in some embodiments, 0.1. Ltoreq. M.ltoreq.1, n is any integer from 10 to 100.
It should be noted that: -OR 2 As the end-capping group, it is selected from the first group, and the explanation of the first group is the same as above, and thus the description thereof is omitted.
In some of these embodiments, X 1 Each occurrence is independently selected from H or alkanyl with 1-5 carbon atoms.
In some of these embodiments, X 1 Each occurrence is independently selected from H or straight-chain alkyl with 1-5 carbon atoms. Non-limiting examples include: H. methyl, ethyl and propyl.
In some of these embodiments, b is selected from 1,2, 3, or 4.
In some of these embodiments, Y is selected from a single bond or O.
In some embodiments, the negative photosensitive resin is represented by formula (1-1) or formula (1-2):
X 11 selected from linear alkyl groups having 1 to 5 carbon atoms, non-limiting examples of which include: methyl, ethyl and propyl.
An embodiment of the present invention also provides a method for preparing the negative photosensitive resin as described above, including the following steps S10 to S40.
S10, carrying out esterification reaction on at least part of first monomer and/or second monomer and dianhydride compound formed by the aromatic tetracarboxylic acid monomer with the ring atom number of 6-60 to prepare a precursor;
the first monomer is an acrylate monomer containing hydroxyl, and the second monomer comprises at least one of a polyol ether monomer containing hydroxyl and a polyol ester monomer containing hydroxyl.
The definitions of the hydroxyl-containing acrylate monomer, the hydroxyl-containing polyol ether monomer and the hydroxyl-containing polyol ester monomer are the same, and are not repeated herein.
It is understood that the precursor mainly includes compounds represented by the following structures:
wherein the content of the first and second substances,
the structure is explained above and will not be described herein.
In some embodiments, the esterification reaction is performed in an ester, amide, sulfone solvent, and further, at least one of γ -butyrolactone, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.
In some embodiments, the esterification reaction is performed in an esterification catalyst, and further, the esterification catalyst is a base catalyst, including but not limited to: triethylamine, dimethylaniline, pyridine, picoline, quinoline and isoquinoline.
In some of these embodiments, the ratio of the first monomer to the second monomer is 1 (0.01 to 0.4).
In some embodiments, the ratio of the total moles of the first monomer and the second monomer to the moles of the dianhydride compound formed from the aromatic tetracarboxylic acid monomer having 6 to 60 ring atoms is 1.5 to 2.5.
The dianhydride compound formed by the aromatic tetraacid monomer has the following structure:
wherein Ar is 1 The same explanations as above are omitted here for brevity.
S20, carrying out polycondensation on the rest of the first monomer and/or the second monomer, the precursor, the third monomer shown in the formula (2) and the aromatic diamine monomer with the ring atom number of 6-60 to prepare the negative photosensitive resin shown in the formula (1);
x in the formula (2) 1 The meanings of Y and b are the same as above, and are not described in detail.
In the polycondensation process, the carboxylic acid group in the precursor is subjected to amide reaction or reaction with the amine group in the third monomer shown in the formula (2) and the aromatic diamine monomer with 6-60 ring atoms to obtain the negative photosensitive resin shown in the formula (1).
In some of these embodiments, the third monomer of formula (2) includes at least one of 4,4' -diaminodiphenyl ether, 4' -diamino-2, 2' -dimethylbiphenyl.
In some embodiments, the polycondensation is carried out in the presence of a dehydration condensation catalyst.
The dehydration condensation catalyst may employ dehydration condensation catalysts commonly used in the art, including but not limited to: n, N' -carbonyldiimidazole, carbodiimide-based condensing agents, onium salt-based condensing agents, and organophosphorus-based condensing agents.
Carbodiimide-based condensing agents include, but are not limited to: dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide (DIC), and 1- (3-dimethylaminopropyl) -3-Ethylcarbodiimide (EDCI); condensing agents for onium salts include, but are not limited to: 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethyluronium Hexafluorophosphate (HATU), benzotriazol-N, N, N ', N' -tetramethyluronium Hexafluorophosphate (HBTU); condensing agents of the organophosphorus type include, but are not limited to: triphenylphosphine-polyhalomethane, triphenylphosphine-hexachloroacetone, triphenylphosphine-NBS, etc.
In a specific example, the dehydration condensation catalyst is at least one of N, N '-dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide, and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
Further, in the process of preparing the negative photosensitive resin represented by formula (1), the precursor is first mixed with a dehydration condensation catalyst to perform activation treatment, and then 4,4' -diaminodiphenyl ether and an aromatic diamine monomer having 6 to 60 ring atoms are added to perform polycondensation.
In the process of producing the negative photosensitive resin represented by formula (1), the precursor is not limited to the method of mixing the precursor with the dehydration condensation catalyst and activating the mixture, and the dehydration condensation catalyst may be added with 4,4' -diaminodiphenyl ether, 4' -diamino-2, 2' -dimethylbiphenyl, and an aromatic diamine monomer having 6 to 60 ring atoms and then activated. In some embodiments, in the process of preparing the negative photosensitive resin represented by formula (1), the precursor is reacted with an acid chloride reagent to prepare an acid chloride of the precursor, and then the third monomer represented by formula (2) and the aromatic diamine monomer having 6 to 60 ring atoms are added to perform polycondensation.
The acid chloride reagents may be those commonly used in the art, including but not limited to: oxalyl chloride and SOCl 2 。
In some examples, the esterification reaction is carried out in an ester, amide, sulfone solvent, further, gamma-butyrolactone, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane.
In some embodiments, the preparing step specifically comprises the following steps: carrying out esterification reaction on a dianhydride compound formed by a first monomer and the aromatic tetracarboxylic acid monomer with the ring atom number of 6-60 to prepare a precursor; and (3) carrying out polycondensation on the precursor, the second monomer, the third monomer shown in the formula (2) and the aromatic diamine monomer with the ring atom number of 6-60 to prepare the negative photosensitive resin shown in the formula (1).
In some embodiments, the preparing step specifically comprises the following steps: performing esterification reaction on a dianhydride compound formed by a first monomer, a second monomer and an aromatic tetracarboxylic acid monomer with 6-60 ring atoms to prepare a precursor; and (2) carrying out polycondensation on the precursor, a third monomer shown in the formula (2) and the aromatic diamine monomer with the ring atom number of 6-60 to prepare the negative photosensitive resin shown in the formula (1).
The mechanical property of the prepared negative photosensitive resin can be further improved by regulating and controlling the adding step of the second monomer.
The invention also provides a photoresist, and the components of the photoresist comprise the negative photosensitive resin.
When the photoresist is used for photoetching, the photoresist has high resolution and good flexibility.
In some embodiments, the photoresist further comprises a photosensitizer, a photocrosslinking agent, a silane coupling agent, a light stabilizer and a solvent.
Further, the sensitizer includes a photoinitiator, a photoinitiator aid, and the like.
In some embodiments, the sensitizer comprises benzophenone, a benzophenone derivative (e.g.: 4,4 '-bis (dimethylamino) benzophenone, dibenzylketone, fluorenone, etc.), acetophenone derivatives (e.g., 2' -diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone, etc.), thioxanthone derivatives (e.g., 2-methylthiothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, etc.), benzil derivatives (e.g., benzil dimethyl ketal, benzil- β -methoxyethyl acetate aldehyde, etc.), benzoin derivatives (e.g., benzoin methyl ether, etc.), 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1, 2-butanedione-2- (O-methoxycarbonyl) oxime, and 1, 3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, 1- [4- (phenylthio) phenyl ] -1, 2-benzoyloctanedione 2- (O-benzoyloxime), 1-phenyl-5-tetrakis, and mixtures of two or more thereof.
The photocrosslinking agent comprises one compound or a mixture of two or more compounds of 2-hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, glycidyl methacrylate, ethylene glycol diether acrylate, tetraethylene glycol dimethacrylate and polyethylene glycol methacrylate.
The silane coupling agent comprises one compound or a mixture of two or more compounds of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidyloxypropyltrimethoxysilane, gamma-glycidyloxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatotrimethoxysilane, 3-isocyanatotriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, vinyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and diphenyldihydroxysilane.
The stabilizer includes at least one of hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, 2, 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, and 2-nitroso-5- (N-ethyl-sulfopropylamino) phenol, 2, 6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt.
The solvent comprises one compound or a mixture of two or more compounds of N-methylpyrrolidone, N '-dimethylacetamide, N' -dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma-butyrolactone, ethyl lactate, cyclopentanone, cyclohexanone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate and butyl acetate.
In a specific example, the components of the photoresist include the negative photosensitive resin, 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyl oxime), tetraethylene glycol dimethacrylate, diphenyldihydroxysilane, 2, 6-di-tert-butyl-p-cresol.
An embodiment of the present invention further provides a negative tone developing method, including the following step S30.
And step S30, coating the photoresist on a substrate, prebaking, photoetching, exposing and developing, dissolving the photoresist in a non-exposure area, and crosslinking and curing the photoresist in an exposure area to form a cured resin to form a pattern layer.
The negative developing method has high resolution and the prepared product has good flexibility.
In some embodiments, the substrate is a silicon wafer.
In some of these embodiments, the exposure is performed in a broad spectrum exposure machine with an exposure energy of 800mJ/cm 2 。
In some embodiments, the developer used in the negative tone development method is cyclopentanone.
In some of these embodiments, after the exposure area is exposed, a step of performing a thermal curing process on the exposed product is further included.
It can be understood that the negative photosensitive resin undergoes a photocuring reaction after exposure to light in the exposed region to give a precured resin, and further undergoes a thermal curing treatment to give a cured resin after complete curing.
An embodiment of the present invention also provides a cured resin prepared from the raw material including the photoresist as described above, or
The above-mentioned cured resin is obtained by the negative developing method as described above.
In some embodiments, the cured resin is prepared by curing a raw material including the photoresist.
In some embodiments, the curing process includes at least one of a photo-curing process and a thermal-curing process.
In some embodiments, the curing process includes a photo-curing process and a thermal-curing process, which are performed sequentially.
In some of these embodiments, the thermal curing process comprises: sequentially curing at 100 deg.C, 150 deg.C, 200 deg.C, 250 deg.C, 300 deg.C, and 350 deg.C for 1 hr.
In some of the embodiments, the photocuring treatment is performed on a broad spectrum exposure machine, and the exposure energy is 800mJ/cm 2 。
While the present invention will be described with respect to particular embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover by the appended claims the scope of the invention, and that certain changes in the embodiments of the invention will be suggested to those skilled in the art and are intended to be covered by the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
Preparation of negative photosensitive resin:
(1) 29.09g (0.09375 mol) of 4,4' -oxydiphthalic anhydride (ODPA) is added to 130g of gamma-butyrolactone under anhydrous and anaerobic conditions for dissolution, and then 1.11g (0.009375 mol) of ethylene glycol monobutyl ether, 25.13g (0.1931 mol) of hydroxyethyl methacrylate and 14.84g (0.1875 mol) of pyridine catalyst are added for reaction for 24 hours at room temperature, so as to obtain a product system containing the negative photosensitive resin.
(2) And under the ice bath condition, 38.69g (0.1875 mol) of mixed solution of N, N' -Dicyclohexylcarbodiimide (DCC) and gamma-butyrolactone is added into the product system of the step (1) by using a constant pressure dropping funnel for activation.
(3) And (3) under the ice bath condition, adding 17.65g (0.088125 mol) of 4,4' -diaminodiphenyl ether diamine (ODA) into the activated system in the step (2) by using a funnel, reacting for 2 hours at room temperature, adding ethanol, stirring, filtering, precipitating, and drying in vacuum to obtain the negative photosensitive resin.
(4) And (3) developing: dissolving the negative photosensitive resin prepared in the step (3) in a mixed solution of N-methyl pyrrolidone and ethyl lactate (volume ratio is 8).
Wherein 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyl oxime) is used as a photoinitiator, tetraethylene glycol dimethacrylate is used as a photocrosslinking agent, diphenyldihydroxysilane is used as a silane coupling agent, and 2, 6-di-tert-butyl-p-cresol is used as a light stabilizer.
Spin coating photoresist on the surface of a silicon wafer, prebaking at 120 deg.C for 3 min to form a photosensitive film layer, and photoetching in a broad-spectrum exposure machine with exposure energy of 800mJ/cm 2 Then, the silicon wafer is placed on a spin coater, cyclopentanone is used as a developing solution, propylene glycol monomethyl ether acetate is used as a rinsing solution, the developing is carried out for 15s at 1000r/s, the developing and rinsing are carried out for 5s at 1000r/s, finally the rinsing is carried out for 20s at 1000r/s by using propylene glycol monomethyl ether acetate, the photoetching resolution is measured by using an optical microscope, the model of the device is Axiolab 5, an optical microscope image of a developed pattern is shown in figure 1, and the resolution result of a pattern layer is shown in table 1.
(5) Mechanical Property measurement
Spin-coating the photoresist solution prepared in the step (4) on the surface of a silicon wafer, prebaking at 120 ℃ for 3 minutes to form a photosensitive film layer, and then carrying out photoetching on the photosensitive film layer by a broad-spectrum exposure machine, wherein the exposure energy is 800mJ/cm 2 Placing the exposed silicon wafer into a high-temperature oven, heating the silicon wafer in a nitrogen atmosphere at a heating rate of 5 ℃/min in a gradient manner, curing the silicon wafer at 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃ and 350 ℃ for 1h respectively, soaking the cured resin film in a 4.9vol% hydrofluoric acid solution for 30 minutes, and drying to obtain a cured resin film, wherein the thickness of the cured resin film is shown in Table 1.
The elongation at break of the cured resin film was measured in accordance with JIS-K6251 using a universal tensile tester at 25 ℃ and 60 RH. The sample was in the form of a strip having a width of 10mm, a specimen length of 50mm and a test rate of 10 mm/min. The 5 samples of the batch cured resin film preparation were allowed to be measured 5 times, and the average value was obtained, and the specific results are shown in Table 1.
The elongation at break is calculated according to the standard specifications: e b ＝(L b -L 0 )/L 0 ×100；
Wherein, E b Elongation at break (%), L 0 Is the initial length, L, of the sample b The length at which it breaks.
Example 2
Preparation of negative photosensitive resin:
(1) 29.09g (0.09375 mol) of 4,4' -oxydiphthalic anhydride (ODPA) is added and dissolved in 130g of gamma-butyrolactone under anhydrous and anaerobic conditions, and 25.13g (0.1931 mol) of hydroxyethyl methacrylate and 22.15g (0.1875 mol) of picoline as a catalyst are reacted for 24 hours at room temperature to obtain a precursor product system.
(2) And dropwise adding 23.66g (0.1875 mol) of mixed solution of N, N' -Diisopropylcarbodiimide (DIC) and gamma-butyrolactone into the product system obtained in the step (1) by using a constant pressure dropping funnel under the ice bath condition for activation.
(3) And (3) adding 19.90g (0.09375 mol) of 4,4 '-diamino-2, 2' -dimethylbiphenyl (M-Tolidine) and 4.28g (0.05625 mol) of ethylene glycol monomethyl ether into the activated system in the step (2) by using a funnel under an ice bath condition, reacting for 2 hours at room temperature, adding ethanol, stirring, filtering, precipitating, and drying in vacuum to obtain the negative photosensitive resin.
(4) And (3) developing: dissolving the prepared negative photosensitive resin in an N-methyl pyrrolidone solution, and adding a photoinitiator, a photocrosslinking agent, a silane coupling agent and a light stabilizer, wherein the mass ratio of the negative photosensitive resin to the photoinitiator, the photocrosslinking agent, the silane coupling agent, the light stabilizer and the N-methyl pyrrolidone is (5).
Wherein 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyl oxime) is used as a photoinitiator, 2-hydroxyethyl methacrylate is used as a photocrosslinking agent, diphenyl dihydroxyl silane is used as a silane coupling agent, and 1-nitroso-2-naphthol is used as a light stabilizer.
Spin coating photoresist on the surface of a silicon wafer, prebaking at 120 deg.C for 3 min to form a photosensitive film layer, and photoetching in a broad-spectrum exposure machine with exposure energy of 800mJ/cm 2 Then the silicon chip is placed on a spin coater and is developed for 25s at 1000r/s by using cyclopentanone as a developing solution and propylene glycol monomethyl ether acetate as a rinsing solution, and the developing solution and the rinsing solution are carried outWashing at 1000r/s for 5s, finally rinsing with propylene glycol monomethyl ether acetate as rinsing solution at 1000r/s for 20s, measuring the photoetching resolution by using an optical microscope, wherein the model of the apparatus is Axiolab 5, and an optical microscope image of a developed pattern is shown in FIG. 2, and the resolution results of a pattern layer are shown in Table 1.
The rest of the procedure was the same as in example 1.
Example 3
Preparation of negative photosensitive resin:
(1) 29.09g (0.09375 mol) of 4,4 '-oxydiphthalic anhydride (ODPA) was dissolved in 130g of N, N' -dimethylacetamide under anhydrous and anaerobic conditions, and then 0.3131g (1.93 mmol) of dipropylene glycol monoethyl ether, 25.13g (0.1931 mol) of hydroxyethyl methacrylate and 14.84g (0.1875 mol) of pyridine as a catalyst were added and reacted at room temperature for 24 hours to obtain a precursor product system.
(2) Under ice bath conditions, 38.69g (0.1875 mol) of a mixed solution of N, N '-Dicyclohexylcarbodiimide (DCC) and N, N' -dimethylacetamide was added dropwise to the product system of step (1) using a constant pressure dropping funnel to activate.
(3) And (3) under the ice bath condition, adding 17.65g (0.088125 mol) of 4,4' -diaminodiphenyl ether diamine (ODA) into the activated system in the step (2) by using a funnel, reacting for 2 hours at room temperature, adding ethanol, stirring, filtering, precipitating, and drying in vacuum to obtain the negative photosensitive resin.
(4) Preparing and developing photoresist: dissolving the prepared negative photosensitive resin in an N-methyl pyrrolidone solution, and adding a photoinitiator, a photocrosslinking agent, a silane coupling agent and a light stabilizer, wherein the mass ratio of the negative photosensitive resin to the photoinitiator, the photocrosslinking agent, the silane coupling agent, the light stabilizer and the N-methyl pyrrolidone is (5).
Wherein, the benzil dimethyl ketal is a photoinitiator, the tetraethylene glycol dimethacrylate is a photocrosslinking agent, the diphenyl dihydroxy silane is a silane coupling agent, and the 1-nitroso-2-naphthol is a light stabilizer.
Spin coating photoresist on the surface of a silicon wafer, prebaking at 120 ℃ for 3 minutes to form a photosensitive film layer, and then placing the photosensitive film layer on a broad-spectrum exposure machine for photoetching, wherein the exposure energy is 800mJ/cm 2 Then, the silicon wafer is placed on a spin coater, cyclopentanone is used as a developing solution, propylene glycol monomethyl ether acetate is used as a rinsing solution, the developing is carried out for 25s at 1000r/s, the developing and rinsing are carried out for 5s at 1000r/s, finally the rinsing is carried out for 20s at 1000r/s by using propylene glycol monomethyl ether acetate, and developed patterns are obtained, and the results of pattern resolution are shown in table 1.
The rest of the procedure was the same as in example 1.
Example 4
Preparation of negative photosensitive resin:
(1) 30.21g (0.09375 mol) of 3,3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) 130g of N-methylpyrrolidone (NMP) is added under anhydrous and anaerobic conditions for dissolution, and then 0.9759g (0.009375 mol) of ethylene glycol monoacetate, 25.13g (0.1931 mol) of hydroxyethyl methacrylate and 14.84g (0.1875 mol) of pyridine catalyst are added for reaction at room temperature for 24 hours to obtain a precursor product system.
(2) And adding a mixed solution of 35.94g (0.1875 mol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI) and N-methylpyrrolidone (NMP) dropwise into the product system obtained in the step (1) under ice-bath conditions by using an isopiestic dropping funnel for activation.
(3) And (3) adding 25.76g (0.08812 mol) of 1, 3-bis (4-aminophenoxy) benzene (TPE-R) into the activated system obtained in the step (2) by using a funnel under an ice bath condition, reacting at room temperature for 2 hours, adding ethanol, stirring, filtering, precipitating and drying in vacuum to obtain the negative photosensitive resin.
(4) Preparing and developing photoresist: dissolving the negative photosensitive resin prepared in the step 1 in an N-methyl pyrrolidone solution, and adding a photoinitiator, a photocrosslinking agent, a silane coupling agent and a light stabilizer, wherein the mass ratio of the negative photosensitive resin to the photoinitiator, the photocrosslinking agent, the silane coupling agent, the light stabilizer and the N-methyl pyrrolidone is 5.
Wherein 2-hydroxy-2-methyl propiophenone is taken as a photoinitiator, tetraethylene glycol dimethacrylate is taken as a photocrosslinking agent, diphenyl dihydroxy silane is taken as a silane coupling agent, and 1-nitroso-2-naphthol is taken as a light stabilizer.
Spin coating photoresist on the surface of silicon wafer, prebaking at 120 deg.C for 3 minForming a photosensitive film layer, and then placing the photosensitive film layer on a broad-spectrum exposure machine for photoetching, wherein the exposure energy is 800mJ/cm 2 Then, the silicon wafer is placed on a spin coater, cyclopentanone is used as a developing solution, propylene glycol monomethyl ether acetate is used as a rinsing solution, the silicon wafer is developed for 25s at 1000r/s, the silicon wafer is developed and rinsed for 5s at 1000r/s, finally the silicon wafer is rinsed for 20s at 1000r/s by using the propylene glycol monomethyl ether acetate as the rinsing solution, developed patterns are obtained, and the resolution results of the pattern layer are shown in table 1.
The remaining procedure was the same as in example 1.
Example 5
Preparation of negative photosensitive resin:
(1) 27.58g (0.09375 mol) of 3, 4' -biphenyltetracarboxylic dianhydride (BPDA) is added to 130g of gamma-butyrolactone to dissolve the gamma-butyrolactone under anhydrous and anaerobic conditions, and then 3.8892g (0.02815 mol) of ethylene glycol phenyl ether, 25.13g (0.1931 mol) of hydroxyethyl methacrylate and 14.84g (0.1875 mol) of pyridine catalyst are added to react for 24 hours at room temperature to obtain a precursor product system.
(2) And under the ice bath condition, 38.69g (0.1875 mol) of mixed solution of N, N' -Dicyclohexylcarbodiimide (DCC) and gamma-butyrolactone is added into the product system of the step (1) dropwise by using a constant pressure dropping funnel for activation.
(3) And (3) adding 25.76g (0.08812 mol) of 1, 4-bis (4-aminophenoxy) benzene (TPE-Q) into the activated system in the step (2) by using a funnel under the ice bath condition, reacting for 2 hours at room temperature, adding ethanol, stirring, filtering, precipitating, and drying in vacuum to obtain the negative photosensitive resin.
(4) Preparing and developing photoresist: dissolving the prepared negative photosensitive resin in an N-methyl pyrrolidone solution, and adding a photoinitiator, a photocrosslinking agent, a silane coupling agent and a light stabilizer, wherein the mass ratio of the negative photosensitive resin to the photoinitiator, the photocrosslinking agent, the silane coupling agent, the light stabilizer and the mixed solution is (5.2).
Wherein 4, 4-bis (dimethylamino) benzophenone is taken as a photoinitiator, tetraethylene glycol dimethacrylate is taken as a photocrosslinking agent, diphenyldihydroxy silane is taken as a silane coupling agent, and 4-methoxyphenol is taken as a light stabilizer.
Spin coating photoresist on the surface of a silicon wafer, firstlyPrebaking at 120 deg.C for 3 min to form photosensitive film, and photoetching in a broad-spectrum exposure machine with exposure energy of 800mJ/cm 2 Then, the silicon wafer is placed on a spin coater, cyclopentanone is used as a developing solution, propylene glycol monomethyl ether acetate is used as a rinsing solution, the silicon wafer is developed for 30s at 1000r/s, the silicon wafer is developed and rinsed for 5s at 1000r/s, finally the silicon wafer is rinsed for 20s at 1000r/s by using the propylene glycol monomethyl ether acetate as the rinsing solution, developed patterns are obtained, and the resolution results of the pattern layer are shown in table 1.
The remaining procedure was the same as in example 1.
Example 6
Preparation of negative photosensitive resin:
(1) Adding 20.45g (0.09375 mol) of phthalic anhydride (PMDA) into 130g of gamma-butyrolactone under anhydrous and anaerobic conditions to dissolve, then adding 9.28g (0.07725 mol) of diethylene glycol monomethyl ether, 22.42g (0.1931 mol) of hydroxyethyl acrylate and 14.84g (0.1875 mol) of catalyst pyridine under ice bath conditions to react for 1-2 hours, and then raising the temperature to room temperature to react for 24 hours to obtain a precursor product system.
(2) Under ice bath conditions, 38.69g (0.1875 mol) of a mixed solution of N, N' -Dicyclohexylcarbodiimide (DCC) and gamma-butyrolactone is added dropwise to the product system of the step (1) by using a constant pressure dropping funnel for activation.
(3) And (3) under the ice bath condition, alternately adding 15.02g (0.07501 mol) of 4,4 '-diaminodiphenyl ether diamine (ODA) and 6.91g (0.01876 mol) of 4,4' -bis (4-aminophenoxy) biphenyl (BAPB) into the activated system in the step (2) by using a funnel, reacting for 2 hours at room temperature, adding ethanol, stirring, filtering, precipitating, and drying in vacuum to obtain the negative photosensitive resin.
(4) Preparing and developing photoresist: dissolving the negative photosensitive resin prepared in the step 1 in an N-methyl pyrrolidone solution, and adding a photoinitiator, a photocrosslinking agent, a silane coupling agent and a light stabilizer, wherein the mass ratio of the negative photosensitive resin to the photoinitiator, the photocrosslinking agent, the silane coupling agent, the light stabilizer and the mixed solution is (5).
Wherein 1-phenyl-1, 2-butanedione-2- (o-methoxycarbonyl) oxime is taken as a photoinitiator, ethylene glycol diethyl ether methacrylate is taken as a photocrosslinking agent, gamma-aminopropyltrimethoxysilane is taken as a silane coupling agent, and 1-nitroso-2-naphthol is taken as a light stabilizer.
Spin coating photoresist on the surface of a silicon wafer, prebaking at 120 deg.C for 3 min to form a photosensitive film layer, and photoetching in a broad-spectrum exposure machine with exposure energy of 800mJ/cm 2 Then, the silicon wafer is placed on a spin coater, cyclopentanone is used as a developing solution, propylene glycol monomethyl ether acetate is used as a rinsing solution, the silicon wafer is developed for 30s at 1000r/s, the silicon wafer is developed and rinsed for 5s at 1000r/s, finally the silicon wafer is rinsed for 20s at 1000r/s by using the propylene glycol monomethyl ether acetate as the rinsing solution to obtain a developed pattern, and the resolution result of the pattern layer is shown in table 1.
The rest of the procedure was the same as in example 1.
Example 7
Step 1: preparation of negative photosensitive resin:
(1) 29.09g (0.09375 mol) of 4,4' -oxydiphthalic anhydride (ODPA) is added to 130g of gamma-butyrolactone under anhydrous and anaerobic conditions for dissolution, and then 0.9764g (0.009375 mol) of propylene glycol monoethyl ether, 27.84g (0.1931 mol) of 2-hydroxypropyl methacrylate and 14.84g (0.1875 mol) of pyridine catalyst are added for reaction at room temperature for 24 hours to obtain a precursor product system.
(2) Under ice bath conditions, 23.41g (0.1969 mol) of SOCl was added dropwise to the product system of step (1) using an isopiestic dropping funnel 2 Stirring the mixture to react for 2h, and removing excessive SOCl by reduced pressure distillation after the reaction is finished 2 。
(3) And (3) adding 17.65g (0.088125 mol) of 4,4' -diaminodiphenyl ether diamine (ODA) into the activated system in the step (2) by using a funnel under the ice bath condition, reacting for 2 hours at room temperature, adding ethanol, stirring, filtering, precipitating, and drying in vacuum to obtain the negative photosensitive resin.
The rest of the procedure was the same as in example 1.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that: the step (1) is as follows:
29.09g (0.09375 mol) of 4,4' -oxydiphthalic anhydride (ODPA) was added under anhydrous and anaerobic conditions to dissolve in 130g of gamma-butyrolactone, and then 25.13g (0.1931 mol) of hydroxyethyl methacrylate was added to react with 14.84g (0.1875 mol) of pyridine as a catalyst at room temperature for 24 hours, to obtain a product system containing a negative photosensitive resin.
Other steps and conditions were the same as in example 1. The optical micrograph of the developed pattern obtained in comparative example 1 is shown in FIG. 3, and the other test results are shown in Table 1.
Comparative example 2
Comparative example 2 is substantially the same as example 2 except that: the step (3) is as follows:
and (3) under the ice bath condition, reacting 19.90g of 4,4 '-diamino-2, 2' -dimethyl biphenyl (M-Tolidine) in the activated system in the step (2) for 2 hours at room temperature by using a funnel, adding ethanol, stirring, filtering, precipitating and drying in vacuum to obtain the negative photosensitive resin.
Other steps and conditions were the same as in example 2. The optical microscope photograph of the developed pattern obtained in comparative example 2 is shown in FIG. 4, and the other test results are shown in Table 1.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that: in step (1), ethylene glycol monomethyl ether was replaced with 0.9578g (0.009375 mol) of n-hexanol.
The other conditions and procedures were the same as in example 1.
The test results of the examples and comparative examples are shown in table 1 below:
TABLE 1
From the results in Table 1, it can be seen that: the negative photosensitive resin of the present application combines high resolution and excellent flexibility.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only show several embodiments of the present invention, and the description thereof is specific and detailed, but not to be construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (13)
1. A negative photosensitive resin, wherein the negative photosensitive resin is represented by formula (1):
wherein, -OR 1 Each occurrence is independently selected from a first group which is an esterified residue of a hydroxyl-containing acrylate monomer and a second group which comprises at least one of an esterified residue of a hydroxyl-containing polyol ether monomer and an esterified residue of a hydroxyl-containing polyol ester monomer; and at least partially-OR 1 Selected from the second group;
X 1 each occurrence is independently selected from H or alkyl with 1-10 carbon atoms, b is selected from any integer of 1-4, and Y is selected from single bond, O or alkane subunit with 1-10 carbon atoms;
m satisfies: 0 < m.ltoreq.1, n represents the degree of polymerization, and x represents the linking site.
2. The negative photosensitive resin according to claim 1, wherein the molar ratio of the first group to the second group in the negative photosensitive resin is 1 (0.01 to 0.4).
3. The negative photosensitive resin of claim 1, wherein Ar is Ar 1 Each occurrence is independently selected from any of the following structures:
wherein R is 3 Each occurrence is independently selected from C1-5 alkane subunit or O;
* Indicates the attachment site.
4. The negative photosensitive resin according to any one of claims 1 to 3, wherein Ar is Ar 1 Each occurrence is independently selected from any of the following structures:
* Indicates the attachment site.
5. The negative photosensitive resin according to any one of claims 1 to 3, wherein the hydroxyl group-containing polyol ether-based monomer comprises at least one of the following structures:
wherein R is 4 Selected from alkyl with 1 to 6 carbon atoms or aryl with 6 to 10 ring atoms, n 1 Is any integer of 1 to 4; and/or
The hydroxyl-containing polyol ester monomer has the following structure:
wherein R is 5 Is selected from alkyl with 1 to 6 carbon atoms or aryl with 6 to 10 ring atoms, and m is any integer of 1 to 4.
6. The negative photosensitive resin according to any one of claims 1 to 3, wherein the hydroxyl group-containing polyol ether-based monomer comprises at least one of the following structures:
wherein n is 1 Is any integer of 1 to 4; and/or
The hydroxyl-containing polyol ester monomer comprises at least one of the following structures:
wherein m is an integer of 1 to 4.
7. The negative photosensitive resin according to any one of claims 1 to 3, wherein the hydroxyl group-containing acrylate monomer comprises at least one of the following structures:
wherein n is 2 Is any integer of 1 to 4.
8. The negative photosensitive resin according to any one of claims 1 to 3, wherein Ar is Ar 2 Each occurrence is independently selected from any of the following structures:
* Indicates the attachment site.
9. A negative photosensitive resin according to any one of claims 1 to 3, wherein 0.1. Ltoreq. M.ltoreq.1, n is any integer of 10 to 100; and/or
X 1 Each occurrence is independently selected from H or alkanyl with 1-5 carbon atoms; and/or
Y is selected from a single bond or O.
10. The method for preparing a negative photosensitive resin according to any one of claims 1 to 9, comprising the steps of:
carrying out esterification reaction on a dianhydride compound formed by at least one part of first monomer and/or second monomer and the aromatic tetracarboxylic acid monomer with the ring atom number of 6-60 to prepare a precursor;
wherein the first monomer is the hydroxyl-containing acrylate monomer, and the second monomer comprises at least one of the hydroxyl-containing polyol ether monomer and the hydroxyl-containing polyol ester monomer
Performing polycondensation on the rest of the first monomer and/or the second monomer, the precursor, the third monomer shown in the formula (2) and the aromatic diamine monomer with the ring atom number of 6-60 to prepare the negative photosensitive resin shown in the formula (1);
11. a photoresist characterized in that the components of the photoresist comprise the negative photosensitive resin according to any one of claims 1 to 9.
12. A method of negative tone development comprising the steps of:
coating the photoresist of claim 11 on a substrate, prebaking, photolithography, exposing, developing, dissolving the photoresist in the non-exposed areas, and curing to form a cured resin in the exposed areas to form a patterned layer.
13. A cured resin prepared from a starting material comprising the photoresist of claim 11, or
The cured resin is prepared by the negative tone development method of claim 12.
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| CN106950800A (en) * | 2016-01-06 | 2017-07-14 | Jnc株式会社 | Photosensitive composition |
| JP2020173431A (en) * | 2019-04-09 | 2020-10-22 | 旭化成株式会社 | Negative type photosensitive resin composition, method for producing polyimide, and method for producing cured relief pattern |
| US20210294213A1 (en) * | 2018-07-31 | 2021-09-23 | Asahi Kasei Kabushiki Kaisha | Negative-type photosensitive resin composition and method for producing polyimide and cured relief pattern using same |
| CN114106326A (en) * | 2021-12-07 | 2022-03-01 | 广东粤港澳大湾区黄埔材料研究院 | Photosensitive resin, photoresist and preparation method and application thereof |
| JP2022154451A (en) * | 2021-03-30 | 2022-10-13 | 味の素株式会社 | Photosensitive resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106950800A (en) * | 2016-01-06 | 2017-07-14 | Jnc株式会社 | Photosensitive composition |
| US20210294213A1 (en) * | 2018-07-31 | 2021-09-23 | Asahi Kasei Kabushiki Kaisha | Negative-type photosensitive resin composition and method for producing polyimide and cured relief pattern using same |
| JP2020173431A (en) * | 2019-04-09 | 2020-10-22 | 旭化成株式会社 | Negative type photosensitive resin composition, method for producing polyimide, and method for producing cured relief pattern |
| JP2022154451A (en) * | 2021-03-30 | 2022-10-13 | 味の素株式会社 | Photosensitive resin composition |
| CN114106326A (en) * | 2021-12-07 | 2022-03-01 | 广东粤港澳大湾区黄埔材料研究院 | Photosensitive resin, photoresist and preparation method and application thereof |
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