CN115128898A

CN115128898A - Photosensitive resin composition and application thereof

Info

Publication number: CN115128898A
Application number: CN202110322165.0A
Authority: CN
Inventors: 韩红彦; 刘永祥; 刘嵩
Original assignee: Beijing Eternal Material Technology Co Ltd
Current assignee: Beijing Eternal Material Technology Co Ltd
Priority date: 2021-03-25
Filing date: 2021-03-25
Publication date: 2022-09-30
Anticipated expiration: 2041-03-25
Also published as: CN115128898B

Abstract

The invention relates to a photosensitive resin composition and application thereof, wherein the photosensitive resin composition comprises the following components: the photosensitive resin comprises alkali soluble resin, a solvent, a photosensitizer and a cross-linking agent, wherein the cross-linking agent has a structure shown in a formula I; according to the invention, the crosslinking agent containing benzyl ether (or benzyl alcohol) and an oxygen heterocyclic group is added into the photosensitive resin composition, the oxygen heterocyclic structure can improve the crosslinking activity at low temperature or improve the crosslinking density at the early stage of curing, so that the fluidity of the photoresist film in the curing process is inhibited, the adverse phenomena of pattern deformation, even pore closing and the like are prevented, the formed cured film has higher barrier property, adhesive force and other properties, and meanwhile, the moisture absorption rate is effectively reduced, so that the gas leakage of the cured film in the device manufacturing process is reduced, and the yield of the device and the reliability in the subsequent use process are improved.

Description

Photosensitive resin composition and application thereof

Technical Field

The invention relates to the technical field of photoetching, in particular to a photosensitive resin composition and application thereof.

Background

With the development of miniaturization, thinning and flexibility of devices such as semiconductors and display panels, it is one of the important issues facing the industry to improve the reliability of products. From the field of materials science, improving the performances of materials such as packaging and interlayer dielectric (such as a heavy wiring layer (RDL layer) and a Bump layer (Bump layer) in a microelectronic device (IC device), radiation protection and insulation layer of the device, a Pixel Definition Layer (PDL) and a Planarization Layer (PLN) in an organic electroluminescent (OLED) device), such as mechanical strength, barrier property, adhesion with a substrate and moisture absorption rate reduction is an effective means for improving the reliability of the device, and is a long-term pursuit in the field of packaging and interlayer dielectric materials at present.

The photosensitive resin composition prepared by compounding alkali soluble resin such as polyamic acid (ester), polyimide, polyhydroxyamide, polybenzoxazole and the like with photosensitive compounds has the characteristics of high resolution, good heat resistance, good chemical resistance and the like, and is widely applied to the fields of packaging of semiconductor devices, interlayer media and the like. However, in the prior art, due to the fact that a relatively high content of hydrophilic groups such as hydroxyl groups and carboxyl groups remain in the cured film of the photosensitive resin, the cured film has relatively high moisture absorption rate and poor barrier property, and the too high moisture absorption rate easily causes a relatively large change in the coefficient of thermal expansion of the material and a relatively large amount of outgassing in the subsequent process, thereby causing phenomena such as cracking of an additional film layer in the subsequent process and the like, reducing the yield of devices, and possibly causing the reliability reduction of the devices in the long-term use process.

In addition, in the thermal curing process of polyamic acid (ester), polyhydroxyamide, and the like, the crosslinking degree and imidization degree are low in the early stage of curing, and the polyamic acid (ester), polyhydroxyamide, and the like have certain fluidity at high temperature, so that the phenomena of closed pores, reduced line width, adhesion between lines, and the like are easily caused, and the yield of device production is reduced.

CN101464631A discloses a photosensitive resin composition for color filters, comprising: (A) carboxyl group-containing propylene-based binder resin; (B) double bond-containing propenyl carboxylate resin; (C) a propenyl photopolymerizable monomer; (D) a photopolymerization initiator; (E) a dye; and (F) a solvent. The photosensitive resin composition has excellent peeling resistance, and thus can be used when a color filter is formed on a TFT array substrate to secure a high aspect ratio. However, a cured film prepared from the photosensitive resin composition has a high moisture absorption rate and is easily deformed at a high temperature, which leads to a reduction in the yield of products.

Therefore, there is a need in the art to develop a novel photosensitive resin composition that can improve the pattern deformation and even the hole closing phenomenon after curing, and ensure the cured film to have excellent barrier property, adhesion and low moisture absorption.

Disclosure of Invention

An object of the present invention is to provide a photosensitive resin composition, and more particularly, to provide a photosensitive resin composition for lithography, which has low fluidity during curing, can prevent the occurrence of adverse phenomena such as pattern deformation and even hole closing, and can form a cured film having high barrier property, adhesion, and other properties, and effectively reduce moisture absorption rate, thereby reducing outgassing of the cured film during device manufacturing process, and improving device yield and reliability during subsequent use.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a photosensitive resin composition, which comprises the following components: the photosensitive resin comprises alkali soluble resin, a solvent, a photosensitizer and a cross-linking agent, wherein the cross-linking agent has a structure shown in a formula I;

in formula I, X is selected from aromatic organic groups;

in the formula I, the-OH is substituted on the benzene ring in the X, and m is more than or equal to 0, such as 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 25, 30, 35, 40, 45, 50, 55 and the like;

in the formula I, R is ₁ An organic group containing an oxygen heterocycle selected from C3 to C20, p is not less than 1, such as 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 25, 30, 35, 40, 45, 50, 55, and the like;

in the formula I, R is ₂ Substituted on the phenyl ring in said X, and said R ₂ Is CH ₂ OC _i H _(2i+1) I is 0 to 8, such as 2,3, 4, 5, 6, 7, etc., n is greater than or equal to 1,e.g., 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 25, 30, 35, 40, 45, 50, 55, etc.;

and m, p, i and n are integers.

The photosensitive resin composition provided by the invention adopts the cross-linking agent containing the benzyl ether (or benzyl alcohol) group and the oxygen heterocyclic group, and in the process of curing the photosensitive resin composition, the oxygen heterocyclic group can quickly generate cross-linking reaction at the early stage of curing, so that the fluidity of a photoresist film is reduced, the phenomena of closed hole, reduced line width, adhesion of patterns and the like are reduced, and the yield and the reliability of products are improved. In addition, the cross-linking agent used in the application reduces the content of hydrophilic groups in the cured film by improving the density of cross-linking groups and reducing the content of hydroxyl groups, thereby reducing the water absorption rate, effectively improving the gas overflow in the subsequent process of the product and improving the use reliability of the device.

In the formula I, X can be a small molecular structure or a polymer chain structure.

Preferably, X is selected from aromatic organic groups of C6-C50, preferably small molecule aromatic organic groups of C6-C50, or X is selected from macromolecule organic groups containing aromatic organic groups;

when X is an aromatic organic group-containing high molecular organic group, the number average molecular weight of X is preferably 1000-50000, for example, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000 and the like, preferably 2000-.

The C6-C50 represents the number of carbon atoms in a small molecule aromatic organic group, and specifically includes but is not limited to C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, C48 and the like.

Preferably, X is selected from any one of the following structures:

wherein the mark of the wavy line represents R ₁ The connecting bond of (1); the-OH and/or R ₂ Substituted at any substitutable position of the benzene ring in the above structure. When m > 0, -OH and R ₂ Substituted at any substitutable position of the phenyl ring in the above structure, when m is 0, R ₂ Substituted at any substitutable position of the benzene ring in the above structure.

Preferably, said R is ₁ At least one organic group selected from an ethylene oxide-containing organic group selected from C3 to C20 (e.g., C20, and C20), an oxetane-containing organic group selected from C20 to C20 (e.g., C20, and the like), or an organic oxazine-containing group selected from C20 to C20 (e.g., C20, and the like), and a combination of at least two or more organic oxazine-containing benzene. "at least two combinations" means that when p is an integer ≧ 2, two or more R's are present ₁ They may be selected from the same group or may be selected from groups different from each other.

Preferably, said R is ₁ Any one or at least two combinations selected from the following groups:

wherein the wavy line represents a bond to said X.

Preferably, the alkali soluble resin includes polyimide and/or a polyimide precursor.

Preferably, the polyimide precursor includes polyamic acid and/or polyamic acid ester.

The polyimide or the precursor resin thereof can be prepared by the polycondensation of a diamine compound and compounds such as dicarboxylic anhydride, tetracarboxylic acid, carboxylic ester, acyl halide and the like in a known manner in the field, for example, the diamine compound is directly polymerized with the dicarboxylic anhydride to obtain polyamic acid, and the polyamic acid is esterified to generate polyamic acid ester; reacting dicarboxylic anhydride with alcohol to generate dicarboxylic diester, reacting with thionyl chloride to generate diacid chloride diester, and then polymerizing with diamine compound to obtain hydroxypolyamide acid ester; dicarboxylic acid diester is generated by reacting dianhydride with alcohol, and then the dicarboxylic acid diester reacts with diamine compound for polymerization in the presence of dehydrating agents such as cyclohexyl carbodiimide, and the like, so as to obtain the hydroxypolyamide acid ester.

The polyimide or the precursor resin thereof of the present invention illustratively comprises a polymer obtained by condensation reaction of a diamine compound having the following structure, and the polymer may be a product obtained by homopolymerization of one compound or copolymerization of different compounds:

wherein r is an integer of 0 to 50, such as 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, etc., preferably an integer of 1 to 20.

Illustrative examples of dicarboxylic acid anhydrides include diphenyl ether dianhydride, 4' - (hexafluoroisopropylene) diphthalic anhydride, bisphenol a diether dianhydride, dibenzyl alcohol dianhydride, 2,3,3',4' -diphenyl ether tetracarboxylic acid dianhydride, hydrogenated pyromellitic dianhydride, benzophenone tetracarboxylic acid dianhydride, cyclobutane tetracarboxylic acid dianhydride, or dianhydride compounds of the following structure:

illustratively, as the tetracarboxylic acid compound, a compound produced by hydrolysis of a dianhydride compound may be mentioned.

Illustratively, as the carboxylic acid ester, there may be mentioned a compound produced by a ring-opening reaction of a dianhydride compound via an alcohol or an alcohol-water mixture.

Illustratively, the alkali-soluble resin may be end-capped at the resin end with an end-capping agent such as a monoamine, an anhydride, an acid chloride, a monocarboxylic acid, an active ester having a reactive group, or the like; in order to further improve the performance, the end-capping reagent can introduce reactive groups, such as alkenyl, alkynyl, benzyl ether and other groups, and a cross-linking reaction occurs in the subsequent curing process, so that the mechanical strength, chemical corrosion resistance and other properties of the film are improved.

Preferably, the alkali-soluble resin has a dissolution rate of 5nm/s to 1000nm/s, for example, 10nm/s, 50nm/s, 100nm/s, 200nm/s, 300nm/s, 400nm/s, 500nm/s, 600nm/s, 700nm/s, 800nm/s, 900nm/s, etc., more preferably 10nm/s to 500nm/s, and still more preferably 20nm/s to 200nm/s, in a 2.38% aqueous tetramethylammonium hydroxide solution.

Preferably, the solvent includes any one or a combination of at least two of γ -butyrolactone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether formate, propylene glycol monoethyl ether formate, propylene glycol methyl ether acetate, ethyl lactate, N-methylpyrrolidone, N-dimethylformamide, or N, N-dimethylacetamide.

Preferably, the sensitizer comprises an organic compound containing a diazonaphthoquinone group.

Preferably, the sensitizer is selected from any one or a combination of at least two of the following compounds:

the R is _a 、R _b 、R _c 、R _d 、R _e Are independently selected from-H and-CH ₃ Any one of-OH, -OQ or phenyl;

t, k and j are respectively and independently selected from integers of 0-5, such as 0, 1, 2,3, 4 or 5;

g is an integer from 0 to 4, such as 0, 1, 2,3 or 4;

f is an integer of 0 to 6, such as 0, 1, 2,3, 4, 5 or 6;

a is an integer from 1 to t, b is an integer from 1 to k, c is an integer from 1 to j, d is an integer from 1 to g, and e is an integer from 1 to f;

q is

Wherein the wavy line represents the bond of the group.

Preferably, the photosensitive resin composition further comprises any one or a combination of at least two of a leveling agent, a coupling agent or a sensitizer. These auxiliaries can improve the uniformity of film thickness during the coating of the composition, adhesion to a substrate, reduction in exposure amount, and the like.

Preferably, the leveling agent includes any one or a combination of at least two of a fluorine-containing surfactant, a surfactant containing a polyethylene glycol structure, or a surfactant containing a siloxane structure. The addition of these leveling agents can improve the degree of planarization of the thin film, improve the thickness variation of the substrate edge film, and the like.

Preferably, the coupling agent comprises a silane coupling agent, preferably an oxygen-containing heterocyclic silane coupling agent. In the curing process, the oxygen heterocyclic group can form a stable molecular bond with the cross-linking agent and the resin through a ring-opening reaction, so that the adhesive force between the photoresist curing film and the substrate is improved.

Preferably, the silane coupling agent includes any one or a combination of at least two of 3-isocyanate propyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl methyldimethoxysilane, 3-ureidopropyl triethoxysilane, 3-aminopropyltrimethoxysilane, (3-glycidoxypropyl) triethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, N- [3- (trimethylsilyl) propyl ] aniline, 3- (2,3 epoxypropoxy) propyl trimethoxysilane, or tridecafluorooctyltrimethoxysilane.

The invention can mix different silane coupling agents for use, thereby improving the adaptability of the composition cured film between different substrates and obtaining the cured film which shows good bonding strength on different substrates.

Preferably, the photosensitive resin composition further comprises any one or a combination of at least two of a photoacid generator, a thermal acid generator, a photobase generator, or a thermal base generator. The addition of these types of substances may promote a crosslinking reaction between the resin and the crosslinking agent and/or a ring-closing reaction of the resin during curing.

Preferably, the thermal decomposition temperature of the thermal acid-generating agent or the thermal alkali-generating agent is 90 to 250 ℃, such as 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, and the like, preferably 100 to 200 ℃.

In view of environmental protection and improvement of device manufacturing process, in order to reduce the manufacturing temperature of the device, the thermal acid generating agent and the thermal alkali generating agent should have lower thermal initial decomposition temperature; in addition, because the boiling point of the solvent in the photosensitive resin composition is usually higher than 90 ℃ under the normal atmospheric pressure and the baking temperature for removing the solvent in the photolithography process is usually between 90 ℃ and 140 ℃ for the requirements of storage stability and low volatility, the thermal decomposition temperature of the thermal acid generator and the thermal alkali generator is preferably between 90 ℃ and 250 ℃, and more preferably between 100 ℃ and 200 ℃.

Preferably, the absorption band of the photoacid generator or the photobase generator is 200 to 450nm, such as 220nm, 240nm, 260nm, 280nm, 300nm, 320nm, 340nm, 360nm, 380nm, 400nm, 420nm, 440nm, etc., preferably 250 to 435 nm. When the absorption band is preferably in the above range, the light quantum efficiency is suitable when exposed to light by an exposure machine using G/H/I line as a light source, and an acid or a base is generated in an appropriate amount, thereby exerting an effect of catalyzing curing.

Preferably, the photoacid generator, thermal acid generator, photobase generator, or thermal base generator is used in an amount of 0.005% to 10%, for example, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc., preferably 0.02% to 3%, more preferably 0.1% to 1%, of the total mass of the photosensitive resin composition.

Preferably, the photoacid generator comprises any one or a combination of at least two of a sulfonium salt, an iodonium salt, or a diazonium salt, preferably any one or a combination of at least two of diazonium sulfate, diazonium hydrochloride, diazonium sulfonate, diazonium fluoroborate, diazonium fluorophosphate, diazonium fluoroantimonate, diazonium perchlorate, triphenylsulfonium hexafluoroantimonate, triphenylthiotriflic acid, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, ditolyiodonium triflate, α - (2-propanesulfonyloxyiminothiophen-3-enyl) -o-methylphenylethyl, or 2- (4-methoxyphenyl) ([ ((4-methylphenyl) sulfonyl) oxy ] imine) acetonitrile, or the like.

Preferably, the thermal acid generator comprises a compound in which the generated acid is a strong acid, preferably any one or a combination of at least two of p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid or trifluoromethanesulfonic acid. Particularly preferred is a thermal acid generator having a thermal decomposition temperature of 90 to 250 ℃ and used in the form of a salt (e.g., an ammonium salt or a sulfonium salt) or a bond such as imide sulfonate.

Preferably, the base generated by the thermal or photobase generator comprises an organic nitrogen-containing compound, preferably any one or a combination of at least two of primary aliphatic amines, tertiary aliphatic amines, primary aromatic amines, tertiary aromatic amines, quaternary ammonium bases, imidazoles, amidines, quinolines, pyridines, or piperidines.

Preferably, the thermogenic base or the photogenic agent is a compound containing no halogen, preferably guanidinium tosylacetate, guanidinium benzenesulfonylacetate, guanidinium phenylpropionate, 9-anthracenemethylpiperidine-1-carboxylate, N-diethylcarbamate, (E) -N-cyclohexyl-3- (2-hydroxyphenyl) acrylamide, (E) -1-piperidino-3- (2-hydroxyphenyl) -2-propen-1-one, 9-anthracenemethylpiperidine-N-cyclohexylcarbamate, guanidino-2- (3-benzoylphenyl) propionic acid, 1- (anthraquinone-2-yl) ethylimidazole-1-carboxylic acid, (2-nitrophenyl) methyl-4-hydroxypiperidine-1-carboxylate, tert-butyl ester, or the like, Any one or at least two combinations of (2-nitrophenyl) methyl-4- (methacryloyloxy), 1- (anthraquinone-2-yl) ethyl-N, N-dicyclohexylcarbamate, dicyclohexyl-2- (3-benzoylphenyl) propionic acid, cyclohexyl-2- (3-benzoylphenyl) propionic acid, 9-anthracenemethyl N, N-dicyclohexylcarbamate or 1- (anthraquinone-2-yl) ethyl N-cyclohexylcarbamate. The halogen-free compound is selected to be beneficial to improving the stability of subsequent devices.

Preferably, the alkali soluble resin is added in an amount of 4 to 30 wt.%, e.g., 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, etc., based on 100 wt.% of the total mass of the photosensitive resin composition, preferably 5 to 20 wt.%;

and/or, the photosensitizer is added in an amount of 0.4 wt.% to 20 wt.%, for example 0.5 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, etc., preferably 1 wt.% to 1 wt.%, based on the total mass of the photosensitive resin composition;

and/or, the solvent is added in an amount of 55 wt.% to 95 wt.%, e.g., 56 wt.%, 58 wt.%, 60 wt.%, 62 wt.%, 64 wt.%, 66 wt.%, 68 wt.%, 70 wt.%, 72 wt.%, 74 wt.%, 76 wt.%, 78 wt.%, 80 wt.%, 82 wt.%, 84 wt.%, 86 wt.%, 88 wt.%, 90 wt.%, 92 wt.%, 94 wt.%, etc., based on the total mass of the photosensitive resin composition.

And/or, the crosslinking agent is added in an amount of 0.1 wt.% to 20 wt.%, for example, 0.5 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, etc., preferably 1 wt.% to 10 wt.%, based on the total mass of the photosensitive resin composition, of 100 wt.%.

Preferably, the solids content of the photosensitive resin composition is 5 wt.% to 45 wt.%, e.g., 6 wt.%, 8 wt.%, 10 wt.%, 12 wt.%, 14 wt.%, 16 wt.%, 18 wt.%, 20 wt.%, 22 wt.%, 24 wt.%, 26 wt.%, 28 wt.%, 30 wt.%, 32 wt.%, 34 wt.%, 36 wt.%, 38 wt.%, 40 wt.%, 42 wt.%, 44 wt.%, etc., preferably 8 wt.% to 30 wt.%. Too low solid content is not favorable for forming a continuous film with a certain thickness, and too high solid content may cause too high viscosity and further cause problems of air bubbles generated in the coating process, poor flatness and the like.

In the present invention, the solid content means the percentage of the sum of the masses of all components except the solvent in the photosensitive resin composition to the total mass of the photosensitive resin composition.

Preferably, the total addition amount of the leveling agent, the coupling agent, and the sensitizer is 0.01 wt.% to 0.5 wt.%, for example, 0.05 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, etc., based on the total mass of the photosensitive resin composition, is 100 wt.%.

The second object of the present invention is to provide a cured film obtained by curing the photosensitive resin composition of the first object.

The photosensitive resin composition can form a cured film after coating, prebaking, photoetching, developing and curing, and the cured film is permanently remained in devices such as semiconductors and display panels, has the characteristics of excellent barrier property, mechanical strength, low moisture absorption rate, high temperature resistance, chemical corrosion resistance, high insulating property and the like, and can be used in the fields of interlayer media, pixel segmentation and the like in the fields of semiconductors, flat panel displays and the like.

The present invention also provides a use of the photosensitive resin composition according to the first aspect or the cured film according to the second aspect in a semiconductor device or a display device.

Preferably, the photosensitive resin composition or the cured film is each independently applied to a planarization layer, a stress buffer layer, or a passivation layer of a semiconductor device.

Preferably, the photosensitive resin composition or the cured film is each independently applied to a pixel defining layer and/or a planarizing layer of a display device.

The fourth object of the present invention is to provide a semiconductor device comprising the photosensitive resin composition according to the first object or the cured film according to the second object.

Preferably, the semiconductor device comprises a stress buffer layer and/or a passivation layer, wherein the stress buffer layer and/or the passivation layer contains the photosensitive resin composition of one purpose or the cured film of the second purpose.

The fifth object of the present invention is to provide a display device comprising the photosensitive resin composition according to the first object or the cured film according to the second object.

Preferably, the display device includes a pixel defining layer and/or a planarizing layer, and the pixel defining layer and/or the planarizing layer contain the photosensitive resin composition described for one of the objects or the cured film described for two of the objects.

Compared with the prior art, the invention has the following beneficial effects:

the cured film formed by the photosensitive resin composition provided by the invention has high yield, high barrier property, adhesive force and other properties, and the moisture absorption rate is effectively reduced, so that the gas overflow of the cured film in the device manufacturing process is reduced, the bonding strength of the cured film and a substrate can be improved, and the yield of the device and the reliability in the subsequent use process are improved.

The cured film formed by the photosensitive resin composition provided by the invention is soaked in stripping liquid at 40 ℃ for etching for 130s, the film thickness loss is lower than 1%, the film thickness loss when the cured film is soaked in N-methylpyrrolidone at room temperature is lower than 1%, and the moisture absorption rate is less than 1.2%, even less than 1%.

Drawings

FIG. 1 is a topographical view of a photosensitive resin composition provided in example 3 of the present invention after curing.

FIG. 2 is a topographical view of a photosensitive resin composition provided in comparative example 1 of the present invention after curing.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

In the following synthesis examples, the ratio of substituted hydroxyl groups was determined by the hydroxyl value titration method provided in GB/T7383-2007.

Synthesis example 1

Synthesis of Cross-linker 1

Under the atmosphere of nitrogen, 40.4g of the compound 1 is dissolved in anhydrous tetrahydrofuran, 4.8g of solid sodium hydroxide and 0.1g of tetrabutylammonium bromide are added, 18.5g of tetrahydrofuran solution of epoxy chloropropane is dropwise added under the stirring at 50 ℃, after the reaction is carried out for 3 hours, the generated salt and sodium hydroxide are filtered and removed, the product is repeatedly dissolved and precipitated by tetrahydrofuran/deionized water to remove impurities, and the crosslinking agent 1 is obtained by freeze drying.

Hydroxyl value titration was performed on the prepared crosslinker, and 54% of the hydroxyl groups in compound 1 were replaced with propylene oxide groups.

Synthesis example 2

Synthesis of Cross-linker 2

Under the atmosphere of nitrogen, 51.2g of compound 2 is dissolved in anhydrous tetrahydrofuran, 5.6g of solid sodium hydroxide and 0.1g of tetrabutylammonium bromide are added, 18.5g of tetrahydrofuran solution of epoxy chloropropane is dropwise added under the stirring at 50 ℃, after the reaction is carried out for 3 hours, the generated salt and sodium hydroxide are filtered and removed, the product is repeatedly dissolved and precipitated by using tetrahydrofuran/deionized water to remove impurities, and the cross-linking agent 2 is obtained by freeze drying, wherein the average hydroxyl substitution degree is 64%.

Hydroxyl value titration is carried out on the prepared cross-linking agent, and 64 percent of hydroxyl groups in the compound 2 are replaced by propylene oxide groups.

Synthesis example 3

Synthesis of Cross-linker 3

Under the atmosphere of nitrogen, 36.2g of the compound 3 is dissolved in anhydrous tetrahydrofuran, 5.6g of solid sodium hydroxide and 0.1g of tetrabutylammonium bromide are added, 18.5g of tetrahydrofuran solution of epoxy chloropropane is dropwise added under the stirring at 50 ℃, after the reaction is carried out for 3 hours, the generated salt and sodium hydroxide are filtered and removed, the product is repeatedly dissolved in tetrahydrofuran/deionized water and precipitated to remove impurities, and the cross-linking agent 3 is obtained by freeze drying.

Hydroxyl value titration is carried out on the prepared cross-linking agent, and 66 percent of hydroxyl groups in the compound 3 are replaced by propylene oxide groups.

Synthesis example 4

Synthesis of Cross-linker 4

Under the atmosphere of nitrogen, 37.6g of the compound 4 is dissolved in anhydrous tetrahydrofuran, 5.3g of solid sodium hydroxide and 0.1g of tetrabutylammonium bromide are added, 18.5g of tetrahydrofuran solution of epoxy chloropropane is dropwise added under the stirring at 50 ℃, after the reaction is carried out for 3 hours, the generated salt and sodium hydroxide are filtered and removed, the product is repeatedly dissolved in tetrahydrofuran/deionized water and precipitated to remove impurities, and the cross-linking agent 4 is obtained by freeze drying.

Hydroxyl value titration was performed on the prepared crosslinker, and 60% of the hydroxyl groups in compound 4 were replaced with propylene oxide groups.

Synthesis example 5

Synthesis of the crosslinking agent 5

Under the atmosphere of nitrogen, 56.8g of the compound 5 is dissolved in anhydrous tetrahydrofuran, 5.6g of solid sodium hydroxide and 0.1g of tetrabutylammonium bromide are added, 18.5g of tetrahydrofuran solution of epoxy chloropropane is dropwise added under the stirring at 50 ℃, after the reaction is carried out for 3 hours, the generated salt and sodium hydroxide are filtered and removed, the product is repeatedly dissolved in tetrahydrofuran/deionized water and precipitated to remove impurities, and the cross-linking agent 5 is obtained by freeze drying.

The prepared cross-linking agent was titrated for hydroxyl value, and 62% of the hydroxyl groups in compound 5 were replaced with propylene oxide groups.

Synthesis example 6

Synthesis of Cross-linker 6

Dissolving 44.8g of compound 6 in anhydrous tetrahydrofuran under nitrogen atmosphere, adding 6g of solid sodium hydroxide and 0.1g of tetrabutylammonium bromide, dropwise adding 18.5g of tetrahydrofuran solution of epoxy chloropropane under stirring at 50 ℃, filtering to remove generated salt and sodium hydroxide after reacting for 3 hours, repeatedly dissolving and precipitating the product with tetrahydrofuran/deionized water to remove impurities, and freeze-drying to obtain the cross-linking agent 6.

The prepared cross-linking agent was titrated for hydroxyl number, and 65% of the hydroxyl groups in compound 6 were replaced with propylene oxide groups.

Synthesis example 7

Synthesis of the crosslinking agent 7

Dissolving 46.1g of compound 7 in anhydrous tetrahydrofuran under a nitrogen atmosphere, adding 4.8g of solid sodium hydroxide and 0.1g of tetrabutylammonium bromide, dropwise adding 18.5g of tetrahydrofuran solution of epoxy chloropropane under stirring at 50 ℃, filtering to remove generated salt and sodium hydroxide after reacting for 3 hours, repeatedly dissolving and precipitating the product with tetrahydrofuran/deionized water to remove impurities, and freeze-drying to obtain the cross-linking agent 7.

The prepared crosslinker was titrated for hydroxyl value, and 53% of the hydroxyl groups in compound 7 were replaced with propylene oxide groups.

Synthesis example 8

Synthesis of Cross-linker 8

Under the atmosphere of nitrogen, 51.2g of compound 2 is dissolved in anhydrous tetrahydrofuran, 5.6g of solid sodium hydroxide and 0.1g of tetrabutylammonium bromide are added, 21g of toluene solution of 3-chloromethyl oxetane is dropwise added under stirring at 100 ℃, after 5 hours of reaction, generated salt and sodium hydroxide are removed by filtration, toluene is removed by freeze drying, the product is repeatedly dissolved and precipitated by tetrahydrofuran/deionized water to remove impurities, and the cross-linking agent 8 is obtained by freeze drying.

The prepared crosslinking agent was subjected to hydroxyl value titration, and 60% of the hydroxyl groups in compound 2 were substituted with 3-methyleneoxetane groups.

Synthesis example 9

Synthesis of Cross-linker 9

52g of phenolic novolac resin (number average molecular weight 3000, hydroxyl equivalent 104g/eq) is weighed and dissolved in anhydrous tetrahydrofuran, 12g of solid sodium hydroxide and 0.1g of tetrabutylammonium bromide are added, a tetrahydrofuran solution containing 34g of 1-chloromethyl-4-methoxymethyl-benzene and 27.7g of epichlorohydrin is added dropwise under continuous stirring at 50 ℃, after 3 hours of reaction, the generated salt and sodium hydroxide are removed by filtration, and after repeated dissolution and precipitation by tetrahydrofuran/water to remove impurities, the crosslinking agent 9 with the following structure is obtained by freeze drying.

Hydroxyl value titration was performed on the prepared crosslinking agent 9, and 64% of the hydroxyl groups in the phenol resin were substituted.

Synthesis example 10

Synthesis of Cross-linking agent 10

60g of 4-hydroxystyrene and 80g of 3- (methoxymethyl) -5-vinylphenol were weighed out and dissolved in 360mL of ethanol, 200mL of deionized water, 0.7g of dodecylmercaptan and 0.7g of azobisisobutyronitrile were slowly added to the system, and the temperature was raised to 70 ℃ with strong stirring for polymerization for 3 hours. The resulting emulsion was poured into 1L of deionized water, filtered and dried to give hydroxystyrene, 3- (methoxymethyl) -5-vinylphenol copolymer, number average molecular weight 3200 (Viscotek gel permeation chromatography, Marwin, D6000M column), hydroxyl equivalent 140.5 g/eq.

70g of the synthesized hydroxystyrene resin is weighed and dissolved in anhydrous tetrahydrofuran, 11g of solid sodium hydroxide and 0.1g of tetrabutylammonium bromide are added, 40g of tetrahydrofuran solution of epoxy chloropropane is dropwise added under the continuous stirring at 50 ℃, after the reaction is carried out for 3 hours, the generated salt and sodium hydroxide are filtered and removed, and after repeated dissolution and precipitation by tetrahydrofuran/water are carried out to remove impurities, the crosslinking agent 10 with the following structure is obtained by freeze drying.

The prepared crosslinking agent 10 was subjected to hydroxyl value titration, and 50% of the hydroxyl groups in the hydroxystyrene, 3- (methoxymethyl) -5-vinylphenol copolymer were substituted with propylene oxide groups.

Synthesis example 11

Synthesis of the crosslinking agent 11

70g of hydroxystyrene and 3- (methoxymethyl) -5-vinylphenol copolymer prepared in Synthesis example 10 was dissolved in methyl isobutyl ketone, 9.3g of aniline and 6.6g of 92% paraformaldehyde were added, and the mixture was reacted at 90 ℃ for 6 hours, after the reaction was completed, the solvent was removed by freeze-drying, and the product was washed with tetrahydrofuran and water by a dissolution precipitation method to remove impurities, and after the solvent was removed by freeze-drying, the following structural crosslinking agent 11 was obtained.

Hydroxyl value titration is carried out on the prepared cross-linking agent 11, and 18 percent of hydroxyl groups in the hydroxystyrene and 3- (methoxymethyl) -5 vinyl phenol copolymer are replaced by benzoxazine groups.

Synthesis example 12

Preparation of polyimide precursor 1

Under the protection of nitrogen, 2.75g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3.65g of 4,4' -diaminodiphenyl sulfone are dissolved in 20mL of N-methylpyrrolidone (NMP), the temperature is reduced to 0 ℃, a mixture of 7.75g of 3,3,4, 4-diphenyl ether tetraanhydride and 22g of anhydrous N-methylpyrrolidone is rapidly added into the reaction system, and the reaction is maintained at 0 ℃ for 5 hours. Heating to 60 ℃, slowly dripping 6.6g N, N-dimethylformamide dimethyl acetal into a reaction system, keeping the temperature at 60 ℃ for reaction for 2h, cooling to room temperature, pouring the reaction solution into 300mL deionized water, filtering, collecting precipitate, and vacuum-drying the precipitate at 50 ℃ for 24h to obtain a polyimide precursor 1(PI-1) with the number-average molecular weight of 6000 (Viscotek gel permeation chromatograph, D6000M chromatographic column, Malvern).

Synthesis example 13

Preparation of polyimide precursor 2

Under the protection of nitrogen, 2.75g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 2.5g of 4,4' -diaminodiphenyl ether are dissolved in 20mL of N-methylpyrrolidone (NMP), the temperature is reduced to 0 ℃, a mixture of 7.75g of 3,3,4, 4-diphenylether tetraanhydride and 22g of anhydrous N-methylpyrrolidone is rapidly added into the reaction system, and the reaction is maintained at 0 ℃ for 5 hours. Heating to 60 ℃, slowly dripping 6.6g N, N-dimethylformamide dimethyl acetal into a reaction system, keeping the temperature at 60 ℃ for reacting for 2 hours, cooling to room temperature, pouring the reaction solution into 300mL of deionized water, filtering, collecting precipitate, and drying the precipitate at 50 ℃ in vacuum for 24 hours to obtain a polyimide precursor 2(PI-2) with the number average molecular weight of 5500 (Viscotek gel permeation chromatograph, D6000M chromatographic column, Malvern). .

Synthesis example 14

Preparation of polyimide precursor 3

In comparison with Synthesis example 12, except that 4,4' - (hexafluoroisopropylene) diphthalic anhydride was used in an equal amount instead of 3,3,4, 4-diphenylether tetraanhydride, polyimide precursor 3(PI-3) was obtained, which had a number average molecular weight of 5800.

Synthesis example 15

Preparation of polyimide precursor 4

Compared with synthetic example 13, the difference is that 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (PI-4) with the same amount of substance is replaced by 3,3,4, 4-diphenyl ether tetraanhydride, and the number average molecular weight is 5500.

Example 1

This example provides a photosensitive resin composition, which is specifically as follows:

polyimide precursor 1(10g), photosensitizer having the following structure (2g), crosslinking agent 1(2g), fluorosurfactant (0.04g), silane coupling agent (0.1g), α - (2-propanesulfonyloxyiminothien-3-enyl) -o-tolylacetonitrile (0.1g), and γ -butyrolactone (85g) were mixed and sufficiently dissolved to obtain photosensitive resin composition C1.

Examples 2 to 11

The only difference from example 1 is that photosensitive resin compositions C2 to C11 were obtained by replacing crosslinking agent 1 with equal mass of crosslinking agents 2 to 11.

Example 12

The only difference from example 1 was that a photosensitive resin composition C12 was obtained by replacing the polyimide precursor 1 with an equal mass of the polyimide precursor 2 and the crosslinking agent 1 with an equal mass of the crosslinking agent 5.

Example 13

The only difference from example 1 was that a photosensitive resin composition C13 was obtained by replacing the polyimide precursor 1 with an equal mass of the polyimide precursor 3 and replacing the crosslinking agent 1 with an equal mass of the crosslinking agent 5.

Example 14

The only difference from example 1 was that a photosensitive resin composition C14 was obtained by replacing the polyimide precursor 1 with an equal mass of the polyimide precursor 4 and the crosslinking agent 1 with an equal mass of the crosslinking agent 5.

Example 15

The only difference from example 1 was that α - (2-propanesulfonyloxyiminothien-3-enyl) -o-tolylacetonitrile was not added, to obtain a photosensitive resin composition C15.

Example 16

The only difference from example 5 was that α - (2-propanesulfonyloxyiminothiophen-3-enyl) -o-methylbenzonitrile was not added, yielding a photosensitive resin composition C16.

Comparative example 1

The only difference from example 3 was that a photosensitive resin composition B1 was obtained by replacing the crosslinking agent 3 with an equal mass of the compound 3.

Comparative example 2

The difference from example 5 was that the crosslinking agent 5 was replaced with an equal mass of the compound 5, to obtain a photosensitive resin composition B2.

Comparative example 3

The only difference from example 16 was that the crosslinking agent 5 was replaced with compound 5, to give a photosensitive resin composition B3.

And (3) performance testing:

(1) and (3) moisture absorption rate test:

the photosensitive resin compositions C1-C16 and B1-B3 were applied to a 4-inch square glass substrate by spin coating, baked to form a film having a thickness of about 5 μm, and exposed to ultraviolet rays without a mask to promote decomposition of the photosensitive compound. After that, the coated glass substrate was placed in a 250 ℃ clean oven and cured under nitrogen protection (oxygen concentration <20ppm) for 60 min.

Placing the cured film in a constant temperature and humidity cabinet with the temperature of 40 +/-2 ℃ and the relative humidity of 80 +/-5% for 24 hours, taking out the film, analyzing the weight loss in a nitrogen atmosphere by using a thermal weight loss analyzer, and calculating the moisture absorption rate of the film, wherein the moisture absorption rate is not less than 1.5, less than 1.5% is qualified, less than 1.2% is good, and less than 1.0% is excellent.

The test results are shown in table 1.

TABLE 1

(2) High temperature deformation test

The test method comprises the following steps: the photosensitive resin compositions C1-C16 and B1-B3 were coated on glass sheets, respectively, and circular holes having a thickness of about 2 μm, a diameter of 5 μm and a spacing of 5 μm were formed by photolithography. After the photo-etched glass sheet is subjected to secondary exposure, the photo-etched glass sheet is placed in an inert oven (the oxygen concentration is less than 20ppm), the photo-etched glass sheet is cured for 1 hour at 250 ℃, and the changes of the appearances of the patterns before and after curing are observed and compared by a scanning electron microscope, wherein the appearance of the photo-sensitive resin composition provided by the embodiment 3 after curing is shown in figure 1, the hole spacing area is flat and has no fluctuation, and the hole diameter has no obvious change, the appearance of the photo-sensitive resin composition provided by the comparative example 3 after curing is shown in figure 2, and the pattern spacing area has obvious fluctuation, and the hole diameter is reduced.

The flatness and the change of the hole diameter of the pattern after curing of different photosensitive resin compositions were observed by a scanning electron microscope, and the results are shown in table 2, where the flatness of the hole-space region and the absence of fluctuation in the hole diameter were recorded as "pass", and the flatness of the pattern-space region and the absence of significant change in the hole diameter were recorded as "difference".

TABLE 2

	Photosensitive resin composition	Quality of graphics
			Example 1	C1	Qualified
Example 2	C2	Qualified
			Example 3	C3	Qualified
Example 4	C4	Qualified
			Example 5	C5	Qualified
Example 6	C6	Qualified
			Example 7	C7	Qualified
Example 8	C8	Qualified
			Example 9	C9	Qualified
Example 10	C10	Qualified
			Example 11	C11	Qualified
Example 12	C12	Qualified
			Example 13	C13	Qualified
Example 14	C14	Qualified
			Example 15	C15	Qualified
Example 16	C16	Qualified
			Comparative example 1	B1	Difference (D)
Comparative example 2	B2	Difference (D)
			Comparative example 3	B3	Difference (D)

As can be seen from the data in tables 1 and 2, compared with the prior art, the present invention effectively reduces the content of hydrophilic groups in the photoresist cured film by adding the crosslinking agent containing benzyl ether (or benzyl alcohol) groups and oxirane groups and regulating the degree of crosslinking reaction and the crosslinking reaction speed, and reduces the large deformation of the pattern caused by poor degree of crosslinking reaction during the curing process, thereby obtaining a photoresist film with good flatness and pattern quality, and significantly improving the pattern quality and effectively increasing the yield in the device manufacturing process.

The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. A photosensitive resin composition, characterized in that it comprises the following components: the photosensitive resin comprises an alkali-soluble resin, a solvent, a photosensitizer and a cross-linking agent, wherein the cross-linking agent has a structure shown in a formula I;

in formula I, X is selected from aromatic organic groups;

in the formula I, the-OH is substituted on a benzene ring in the X, and m is more than or equal to 0;

in the formula I, R is ₁ Is selected from C3-C20 organic groups containing oxygen heterocycle, and p is more than or equal to 1;

in the formula I, R is ₂ Substituted on the phenyl ring in said X, and said R ₂ Is CH ₂ OC _i H _(2i+1) ，0≤i≤8，n≥1；

And m, p, i and n are integers.

2. The photosensitive resin composition according to claim 1, wherein X is selected from an aromatic organic group of C6-C50 or a high molecular organic group containing an aromatic organic group;

when X is a high molecular organic group, the number average molecular weight of X is preferably 1000-.

3. The photosensitive resin composition according to claim 1, wherein X is selected from any one of the following structures:

wherein, the mark of the wavy line represents R ₁ The connecting bond of (1); the-OH and/or R ₂ Substituted at any substitutable position of the benzene ring in the above structure.

4. The photosensitive resin composition according to claim 1, wherein R is ₁ Any one or any combination of at least two of organic groups selected from organic groups containing ethylene oxide of C3-C20, organic groups containing oxetane of C4-C20 or organic groups containing benzoxazine structure of C8-C20.

5. The photosensitive resin composition of claim 1, further comprising any one or a combination of at least two of a leveling agent, a coupling agent, or a sensitizer.

6. The photosensitive resin composition according to claim 1, further comprising any one or a combination of at least two of a photoacid generator, a thermal acid generator, a photobase generator, or a thermal base generator.

7. A photosensitive resin composition according to claim 1, wherein the alkali soluble resin is added in an amount of 4 wt.% to 30 wt.%, preferably 5 wt.% to 20 wt.%, based on 100 wt.% of the total mass of the photosensitive resin composition;

and/or, the addition amount of the photosensitizer is 0.4 wt.% to 20 wt.%, preferably 1 wt.% to 10 wt.%, based on the total mass of the photosensitive resin composition, of 100 wt.%;

and/or, the addition amount of the solvent is 55 wt.% to 95 wt.%, based on the total mass of the photosensitive resin composition, of 100 wt.%;

and/or, the crosslinking agent is added in an amount of 0.1 wt.% to 20 wt.%, preferably 1 wt.% to 10 wt.%, based on the total mass of the photosensitive resin composition, of 100 wt.%.

8. A photosensitive resin composition according to claim 1, wherein said photosensitive resin composition has a solid content of 5 wt.% to 45 wt.%, preferably 8 wt.% to 30 wt.%.

9. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 8.

10. Use of the photosensitive resin composition according to any one of claims 1 to 8 or the cured film according to claim 9 in a semiconductor device or a display device;

preferably, the photosensitive resin composition or the cured film is each independently applied to a planarization layer, a stress buffer layer, or a passivation layer of a semiconductor device;

11. A semiconductor device comprising the photosensitive resin composition according to any one of claims 1 to 8 or the cured film according to claim 9;

preferably, the semiconductor device includes a stress buffer layer and/or a passivation layer containing the photosensitive resin composition of any one of claims 1 to 8 or the cured film of claim 9.

12. A display device comprising the photosensitive resin composition according to any one of claims 1 to 8 or the cured film according to claim 9;

preferably, the display device includes a pixel defining layer and/or a planarizing layer containing the photosensitive resin composition according to any one of claims 1 to 8 or the cured film according to claim 9.