CN115581120A - Polysulfonamide polymers, negative-working photosensitive compositions containing polysulfonamide polymers and uses thereof - Google Patents

Polysulfonamide polymers, negative-working photosensitive compositions containing polysulfonamide polymers and uses thereof Download PDF

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CN115581120A
CN115581120A CN202080100667.2A CN202080100667A CN115581120A CN 115581120 A CN115581120 A CN 115581120A CN 202080100667 A CN202080100667 A CN 202080100667A CN 115581120 A CN115581120 A CN 115581120A
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崔庆洲
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Abstract

The invention discloses a polysulfonamide polymer, a negative photosensitive composition containing the polysulfonamide polymer and application of the negative photosensitive composition. The negative photosensitive composition containing the polysulfonamide polymer comprises the following raw materials in a certain weight ratio: polysulfonamide polymers, photoacid generators, crosslinkers, solvents, and some other components. The composition can prepare a polysulfonamide cured material film under the condition of lower curing temperature (less than or equal to 250 ℃), and the cured material film can be used as a redistribution layer, an interlayer insulating buffer film, a covering coating or a surface protection film material.

Description

Polysulfonamide polymers, negative-working photosensitive compositions containing polysulfonamide polymers and uses thereof Technical Field
The invention relates to a photosensitive dielectric material applied in the field of semiconductors, in particular to a negative photosensitive composition containing a polysulfonamide polymer, a cured product prepared from the negative photosensitive composition and application of the negative photosensitive composition in semiconductor packaging.
Background
Semiconductor chips have been one of the major drivers of scientific and technological progress in the past sixty years, and many technological innovations have relied on the powerful computing power of semiconductor chips and their progressively smaller sizes. Moore's law has been effectively predictive and dominates the scaling of transistors in semiconductor processing, but in recent years transistor miniaturization has become more and more costly after a 28 nm technology node. Furthermore, the physical and chemical limits of the materials make the technical breakthrough of miniaturization of transistors more and more difficult. Future technological advances require the search for new technology breakthrough points. Advanced packaging is considered to be a new technology that is currently most likely to achieve this technological breakthrough. Advanced packaging connects a plurality of chips or packages together through direct means of chip connection, chip connection packaging, package connection packaging and the like, and the optimized system integration not only realizes short-distance rapid transmission between signals, but also effectively reduces energy consumption and heat generation of functional devices. Most importantly, the system integration can reduce a large number of functions to a small area, so that the system integration provides infinite innovation possibility for the current mobile computing innovation mainly based on the smart phone.
Each advanced packaging technology in the existing market will be different, but most of them require the construction of a redistribution layer. These redistribution layers solve the connection problem between the chip, package and motherboard. Redistribution layer materials are typically comprised of copper wire encased in an insulating dielectric material. These copper leads will lead signals into or out of the chip to allow signal transmission between the chip and the outside world. These micron-sized copper leads have been difficult to efficiently fabricate using conventional mechanical methods, and electrochemical deposition methods are becoming the mainstream method for fabricating copper leads with the aid of photosensitive dielectric materials. In addition, these photosensitive dielectric materials remain in the device as permanent insulating materials surrounding the copper leads after the fabrication process is completed. Therefore, the application requires that the insulating material not only has excellent photoetching performance, but also has better insulating performance, mechanical performance, adhesion, high-temperature stability, low water absorption, high chemical corrosion resistance and the like. Due to the above-mentioned comprehensive requirements, materials such as photosensitive Polyimide (PI), polybenzobisoxazole (PBO), benzocyclobutene (BCB) and the like have gradually become the main materials in this field due to their excellent high-temperature-resistant material properties. In addition, the new high-performance insulating material has great prospect in other applications such as interlayer insulating buffer films, covering coatings or surface protection films.
The existing advanced packaging technology process generally combines Epoxy-based EMC (Epoxy Molding Compounds) and lead-free solder material with lower melting point (melting point is approximately 260 ℃ or lower), which requires that subsequent processing steps must avoid using higher post-curing temperature but requires that the material has better long-term stability. The traditional photosensitive polyimide, polybenzoxazole and benzocyclobutene usually require the post-curing temperature of more than or equal to 300 ℃, so the traditional high-temperature resistant materials have larger limitation in the new application. In addition, the conventional materials have the disadvantages of high water absorption, high loss of film thickness, complex process and the like, which further limits the application of the conventional materials in the new field.
Accordingly, there is still inconvenience and disadvantage in the conventional photosensitive composition containing polyimide, polybenzoxazole and benzocyclobutene and cured products prepared therefrom, and further improvement is desired. Therefore, the novel photosensitive material with low-temperature curing capability has great market demand and application prospect. The novel polysulfonamide material is a novel material which is developed under the background and can realize lower curing and forming temperature.
Disclosure of Invention
The main objective of the present invention is to overcome the defects of the existing photosensitive dielectric material, and to provide a novel polysulfonamide polymer mainly used for negative photosensitive dielectric material, wherein the polysulfonamide polymer not only has excellent mechanical properties, but also has the advantages of good insulating property, good adhesion, high temperature stability, low water absorption, high chemical corrosion resistance, etc.
Another main object of the present invention is to provide negative-type photosensitive compositions containing polysulfonamide polymers, which can provide effective crosslinking ability and excellent lithographic performance under low-temperature (250 ℃ or lower) heat treatment conditions, thereby producing cured products having a relief microstructure.
Another object of the present invention is to provide a pattern cured product prepared from the above-mentioned novel photosensitive polysulfonamide polymer composition.
It is still another object of the present invention to provide a use of the cured product in a redistribution layer, an interlayer insulating buffer film, a cap coat or a surface protective film.
It is still another object of the present invention to use the cured product in related electronic products.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. According to the invention, a polysulfonamide polymer of the general formula (1),
Figure PCTCN2020091094-APPB-000001
the polysulfonamide polymer has a repeating unit structural formula as follows, wherein m and n represent the number of structural units in the polymer and are integers of 1-99.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
In the polysulfonamide polymer described above, X1 and X2 in the general formula (1) are divalent aromatic linking groups which may be different or the same and have a group represented by the following general formula (2), (3), or (4);
Figure PCTCN2020091094-APPB-000002
wherein R is 1 ，R 2 ，R 3 ，R 4 Each represents a hydrogen atom or a monovalent organic group;
Figure PCTCN2020091094-APPB-000003
wherein Q is a direct bond or a divalent organic group selected from O, S, CO, SO 2 、Si(CH 3 ) 2 、CH(OH)、(CH 2 ) p (1≤p≤10)、(CF 2 ) q (1≤q≤10)、C(CH 3 ) 2 、C(CF 3 ) 2 Substituted or unsubstituted-o, -m, -p-phenylene;
Figure PCTCN2020091094-APPB-000004
wherein T is a direct bond or a divalent organic group selected from O, S, CO, SO 2 、Si(CH 3 ) 2 、CH(OH)、(CH 2 ) p (1≤p≤10)、(CF 2 ) q (1≤q≤10)、C(CH 3 ) 2 、C(CF 3 ) 2 Substituted or unsubstituted-o, -m, -p-phenylene, wherein R 5 ～R 12 Are identical or different monovalent organic radicals selected from the group consisting of H, CH 3 Or CF 3 ；
Wherein Y in the polysulfonamide polymer of the general formula (1) is a divalent aromatic group selected from the structural units represented by the following formula (5) or (6):
Figure PCTCN2020091094-APPB-000005
wherein U in the general formula (6) is a direct bond or a divalent organic group selected from O, S, CO, SO 2 、Si(CH 3 ) 2 、CH(OH)、(CH 2 ) p (1≤p≤10)、(CF 2 ) q (1≤q≤10)、C(CH 3 ) 2 、C(CF 3 ) 2 Substituted or unsubstituted-o, -m, -p-phenylene.
The aforementioned polysulfonamide polymers, which are block copolymers or random copolymers, have a weight average molecular weight in the range of 5,000 to 200,000.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. A negative-type photosensitive composition containing a polysulfonamide polymer is provided according to the present invention, which includes:
(A) A polysulfonamide polymer;
(B) Photoacid generators: the content thereof in the composition is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the component (a);
(C) A crosslinking agent: the content thereof in the composition is preferably 2 to 50 parts by mass, more preferably 8 to 40 parts by mass, relative to 100 parts by mass of the component (a);
(D) Solvent: the content thereof in the composition is preferably 50 to 800 parts by mass, more preferably 60 to 300 parts by mass, and still more preferably 80 to 220 parts by mass, based on 100 parts by mass of the component (a).
The purpose of the invention and the technical problem to be solved can be further realized by adopting the following technical measures.
The negative photosensitive composition comprising polysulfonamide polymers as described above, wherein component (B) is at least one photoacid generator. The photoacid generator is selected from, but not limited to, ionic compounds including sulfonium, phosphonium, or iodonium salts; the nonionic compound includes an oxime sulfonate, a sulfonate compound, or a quinone diazide compound; or mixtures thereof. From the viewpoint of sensitivity and imaging property, oxime sulfonate compounds are preferable; and/or
Wherein the component (C) contains at least one compound having a-CH 2 Alkoxy compounds/hydroxy compounds of OR (R is a hydrogen atom OR a 1-valent organic group); an epoxy compound; oxetane compounds and vinyl ether compounds, preferably compounds having an alkoxyalkyl group such as a hydroxymethyl group or an alkoxymethyl group; and/or
Wherein the ingredients of said composition are dissolved in a solvent (D) comprising at least one compound selected from the group consisting of: esters, ethers, ether-esters, ketones, ketone-esters, aromatics, and/or halogenated hydrocarbon solvents.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. A negative-type photosensitive composition containing a polysulfonamide polymer according to the present invention is a negative-type photosensitive composition having a relief pattern, which is prepared by a method comprising the steps of:
(a) A step of coating the polysulfonamide polymer composition on a substrate and heating to remove the solvent to form a photosensitive resin film;
(b) A step of pattern-exposing the photosensitive resin film by using a mask;
(c) A step of removing the unexposed area of the coating layer to obtain a resin cured film having a relief pattern, and
(d) And a step of subjecting the relief pattern resin film to a heat curing treatment.
The purpose of the invention and the technical problem to be solved can be further realized by adopting the following technical measures.
The cured product having a relief pattern described above, wherein the temperature of the heat treatment is 250 ℃ or less.
The cured product having a relief pattern is a cured product film having a microstructured relief pattern.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The cured product having a relief pattern according to the present invention is applied to a redistribution layer, an interlayer insulating buffer film, a cap coat or a surface protective film.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the invention, the electronic device comprises the redistribution layer, the interlayer insulating buffer film, the covering coating or the surface protection film.
Accordingly, the present invention discloses a polysulfonamide polymer, a negative photosensitive composition containing the polysulfonamide polymer, and applications thereof. The negative photosensitive composition containing the polysulfonamide polymer comprises the following raw materials in a certain weight ratio: polysulfonamide polymers, photoacid generators, crosslinking agents, solvents, and some other components. The composition can prepare a polysulfonamide cured film under the condition of lower curing temperature (less than or equal to 250 ℃), and the cured film can be used as a redistribution layer, an interlayer insulating buffer film, a covering coating or a surface protection film material.
By the technical scheme, the negative photosensitive composition containing the polysulfonamide polymers, the cured product prepared from the negative photosensitive composition and the application of the negative photosensitive composition in semiconductor packaging have at least the following advantages:
in view of the relatively high cure temperatures required for conventional photosensitive dielectric materials, novel polysulfonamide compositions are employed in the present invention. As a result, it has been found that such films can be prepared with films having a relief microstructure under relatively low temperature (250 ℃ or lower) heat treatment conditions. By adjusting the proportion of each monomer in the film, each component of the composition and the heat treatment condition, the dissolution speed and the mechanical property of the film and the properties of various other materials can be well regulated, controlled and optimized. In addition, such a resin composition retains the general advantage of excellent adhesion of most negative-type photosensitive materials to substrates. Finally, by using fluorine atom-containing monomers during the polymer synthesis, these new materials will have a significant improvement in reducing the water absorption of the materials, thereby making the cured film prepared from the present compositions more suitable for the current advanced packaging process requirements.
In summary, the technical solution of the present invention has the advantages and practical values mentioned above, and similar designs are not published or used in similar products, but rather are innovative, and it has great improvements in both formulation and function, and has great technical progress, and produces good and practical effects, and has enhanced multiple functions compared with the existing products, so as to be more practical, and thus has a wide industrial utility value, and is a novel, advanced and practical new design.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
Figure 1 is an embodiment of the invention involving the fabrication of a redistribution layer.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments of the polysulfonamide containing polymers, negative photosensitive compositions containing polysulfonamide containing polymers, cured products prepared therefrom, and their use in semiconductor packaging according to the present invention will be given with reference to the accompanying drawings and preferred embodiments.
Hereinafter, the present invention will be described in further detail with reference to synthetic examples of polysulfonamide polymers and examples/comparative examples. The present invention is not limited to these polymer synthesis examples and examples/comparative examples, and those having ordinary knowledge in the art can make various modifications within the technical spirit of the present invention.
1. (A): polysulfonamide polymers
The properties of the polysulfonamide polymers prepared in Synthesis examples 1 to 25 are illustrated below.
Figure PCTCN2020091094-APPB-000006
The polysulfonamide-based polymer having the formula (1) is characterized in that the polymer has a structural formula of a repeating unit represented by the general formula (1), wherein m and n represent the number of structural units in the polymer and are integers of 1 to 99. From the viewpoint of film-forming properties and controlling the dissolution rate, m and n are preferably integers of 5 to 99.
X1 and X2 in the general formula (1) are divalent aromatic linking groups, and they may be different or the same groups represented by the following general formula (2), (3) or (4).
Figure PCTCN2020091094-APPB-000007
Wherein R is 1 ，R 2 ，R 3 ，R 4 Each represents a hydrogen atom or a monovalent organic group such as a methyl group.
Figure PCTCN2020091094-APPB-000008
Wherein Q represents a direct bond or other 2-valent organic group, e.g. O, S, CO, SO 2 、Si(CH 3 ) 2 、CH(OH)、(CH 2 ) p (1≤p≤10)、(CF 2 ) q (1≤q≤10)、C(CH 3 ) 2 、C(CF 3 ) 2 Substituted or unsubstituted-o, -m, -p-phenylene.
Figure PCTCN2020091094-APPB-000009
Wherein T represents a direct bond or other 2-valent organic group, e.g. O, S, CO, SO 2 、Si(CH 3 ) 2 、CH(OH)、(CH 2 ) p (1≤p≤10)、(CF 2 ) q (1≤q≤10)、C(CH 3 ) 2 、C(CF 3 ) 2 Substituted or unsubstituted-o, -m, -p-phenylene. Wherein R is 5 ～R 12 Are identical or different monovalent organic radicals, e.g. H, CH 3 Or CF 3 。
The polysulfonamide polymer described above, wherein Y in the general formula (1) is a divalent aromatic group selected from the structural units represented by the following formula (5) or (6):
Figure PCTCN2020091094-APPB-000010
wherein U in the general formula (6) is a direct bond or other 2-valent organic group selected from O, S, CO and SO 2 、Si(CH 3 ) 2 、CH(OH)、(CH 2 ) p (1≤p≤10)、(CF 2 ) q (1≤q≤10)、C(CH 3 ) 2 、C(CF 3 ) 2 Substituted or unsubstituted-o, -m, -p-phenylene.
The synthesis method of the polysulfonamide polymer is as follows: in an inert atmosphere, dissolving a diamine mixture and 2-methylpyridine in N-methylpyrrolidone, then dropwise adding a sulfonyl chloride monomer (dissolved in the N-methylpyrrolidone) with the molar weight equal to that of the diamine monomer, reacting for 1 hour in an ice bath at 0-5 ℃, settling the obtained polymer solution in a deionized water medium, filtering, and drying in vacuum at 80-120 ℃ to obtain the polysulfonamide polymer.
The above-mentioned polysulfonamide polymers may have a weight average molecular weight of 5,000 to 200,000. Preferably a weight average molecular weight of 10,000 to 120,000. Here, the molecular weight is measured by a Gel Permeation Chromatography (GPC) method and calculated from a standard polystyrene standard curve.
The polysulfonamide polymers described above may be block copolymers or random copolymers. In order to improve the stability of the composition, the main chain end may be capped with a capping agent such as a monoamine or a monoacid chloride compound. The proportion of monoamine to be introduced as the end-capping agent is preferably 0.5 to 30 mol% based on the entire amine component. As monoamines: can be selected from aniline, 2-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene; as the monoacid chloride compound: the monocarboxylic acid such as 3-carboxybenzenesulfonic acid or 4-carboxybenzenesulfonic acid and the monoacid chloride compound obtained by acid chlorination of the carboxyl group thereof may be selected, and the monocarboxylic acid chloride compound obtained by acid chlorination of only one carboxyl group of dicarboxylic acids such as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxylnaphthalene, 1,6-dicarboxylnaphthalene, 1,7-dicarboxylnaphthalene, and 2,6-dicarboxylnaphthalene may be selected, and the active ester compound obtained by reaction of the monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxylimide may be selected. The blocking agent may be one or more of the compounds described above.
The above polysulfonamide polymers are generally developed using an aqueous alkaline solution. Accordingly, polysulfonamide polymers which are soluble in alkaline solvents are preferred. Preparing a solution of a polysulfonamide polymer, spin-coating the solution on a substrate such as a silicon wafer, and drying the substrate by heating to remove the solvent to form a resin film having a thickness of about 10 μm; then dipping the mixture into tetramethylammonium hydroxide aqueous solution at the temperature of between 20 and 25 ℃; the ease with which component (A) dissolves in the alkaline aqueous solution is determined by the time required for the film to dissolve completely.
In addition, the transmittance of the i-line directly affects the resolution of the photosensitive composition during processing. In order to obtain a microstructure relief pattern with the best resolution under the same film thickness condition, the polysulfonamide polymer preferably has a monomer structure containing fluorine atoms with good light transmittance. The fluorine-containing composition is also advantageous in reducing the effect of the solution on the immersion swelling of the film at the time of development to suppress the bleeding from the surface, and also in reducing the water absorption of the composition after curing.
Finally, the stress of a cured film obtained by applying the composition containing the polysulfonamide polymer represented by formula (1) to a substrate and curing the composition by heating is preferably 30MPa or less. If the stress is less than or equal to 30MPa, the wafer warpage can be effectively inhibited after the film is solidified and formed, so that the wafer reworking (wafer reworking) process widely adopted in the current advanced packaging process is suitable for application.
Therefore, in the polysulfonamide-based polymer, from the viewpoint of a combination of light transmittance, water absorption, alkali solubility and stress, X1 and X2 in the general formula (1) are divalent aromatic linking groups, and at least one of them is preferably a structural unit having a trifluoromethyl group and represented by the following general formula (7) and/or a structural unit having a phenyl ether group and represented by the following general formula (8).
Figure PCTCN2020091094-APPB-000011
The polysulfonamide polymer represented by the general formula (1) wherein Y also preferably has a phenylene ether group structural unit represented by the above general formula (8) from the viewpoint of stress and alkali solubility.
The following are preferred synthetic examples of polysulfonamide polymers of the present invention.
Synthesis example 1:
in a four-necked flask with mechanical stirrer, thermometer and atmosphere of high purity nitrogen, 2,2 '-bis (trifluoromethyl) diaminobiphenyl (50 mmol), 4,4' -diaminodiphenyl ether (50 mmol), 2-methylpyridine (300 mmol) and anhydrous N-methyl-2-pyrrolidone (NMP) (47.25 g) were charged, stirred until completely dissolved (solution became clear) and cooled to-10 ℃. The solution was kept at a temperature range of-10 to-5 ℃ and a mixture of 4,4' -bis (sulfonyl chloride) diphenyl ether (100 mmol) and anhydrous N-methyl-2-pyrrolidone (42.00 g), which had been dissolved, was added dropwise thereto over a half hour, and then stirring was continued for 1 hour while keeping the solution at a temperature of 0 to 5 ℃. The resulting reaction solution was slowly dripped into about 8 liters of water, and after settling and recovering precipitates by filtration and repeating the same procedure, washing with pure water was repeated 3 times to obtain a wet product. And dried in a vacuum oven at 80 ℃ for more than 24h to obtain the final product. The resulting random copolymer was named Polymer-1 and its structural formula is shown below. m and n are the respective numbers of repeating units, and the mole fractions of the structural units are m/(m + n) =0.5 and n/(m + n) =0.5, respectively.
(Polymer-1)
Figure PCTCN2020091094-APPB-000012
Synthesis examples 2 to 3:
synthesis methods of Polymer-2 and Polymer-3 with reference to Synthesis example 1, except that the molar fractions of the diamine monomers were adjusted to: 2,2 '-bis (trifluoromethyl) diaminobiphenyl (75 mmol), 4,4' -diaminodiphenyl ether (25 mmol) (synthesis example 2) and 2,2 '-bis (trifluoromethyl) diaminobiphenyl (25 mmol), 4,4' -diaminodiphenyl ether (75 mmol) (synthesis example 3). Other conditions/procedures were exactly the same as those in Synthesis example 1. Thus, the chemical formulae of Polymer-2 and Polymer-3 are identical to Polymer-1, except that the molar fraction m/(m + n) is changed: 3 respectively: 1 (Synthesis example 2: polymer-2) and 1:3 (Synthesis example 3: polymer-3).
Synthesis example 4
In a four-necked flask equipped with a mechanical stirrer, a thermometer and a high purity nitrogen atmosphere, 2,2 '-bis (trifluoromethyl) diaminobiphenyl (47.5 mmol), 4,4' -diaminodiphenyl ether (47.5 mmol), m-aminophenol (10 mmol), 2-methylpyridine (300 mmol) and anhydrous N-methyl-2-pyrrolidone (NMP) (47.25 g) were charged, stirred until completely dissolved (the solution became clear), and cooled to-10 ℃. The solution was kept at a temperature range of-10 to-5 ℃ and a mixture of 4,4' -bis (sulfonyl chloride) diphenyl ether (100 mmol) and anhydrous N-methyl-2-pyrrolidone (42.00 g), which had been dissolved, was added dropwise thereto over a half hour, and then stirring was continued for 1 hour while keeping the solution at a temperature of 0 to 5 ℃. The resulting reaction solution was slowly dripped into about 8 liters of water, and after settling and filtering to recover precipitates and repeating the same process, washing with pure water was repeated 3 times to obtain a wet product. And dried in a vacuum oven at 80 ℃ for more than 24h to obtain the final product. The resulting random copolymer was named Polymer-4 and its structural formula is shown below. m and n are the respective numbers of repeating units, and the mole fractions of the structural units are m/(m + n) =0.5 and n/(m + n) =0.5, respectively.
(Polymer-4)
Figure PCTCN2020091094-APPB-000013
Synthesis examples 5 to 6:
synthesis methods of Polymer-5 and Polymer-6 with reference to Synthesis example 4, except that the molar fractions of the diamine monomers were adjusted to: 2,2 '-bis (trifluoromethyl) diaminobiphenyl (71.25 mmol), 4,4' -diaminodiphenyl ether (23.75 mmol) (synthesis example 5) and 2,2 '-bis (trifluoromethyl) diaminobiphenyl (23.75 mmol), 4,4' -diaminodiphenyl ether (71.25 mmol) (synthesis example 6). Other conditions/procedures were exactly the same as in Synthesis example 4. Thus, the chemical formulae of Polymer-5 and Polymer-6 are identical to Polymer-4, except that the molar fraction m/(m + n) is varied to be 3:1 (Synthesis example 5: polymer-5) and 1:3 (Synthesis example 6: polymer-6).
Synthesis example 7
In a four-necked flask with a mechanical stirrer, a thermometer and a high purity nitrogen atmosphere, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (50 mmol), 4,4' -diaminodiphenyl ether (50 mmol), 2-methylpyridine (300 mmol) and anhydrous N-methyl-2-pyrrolidone (NMP) (47.25 g) were charged, stirred until completely dissolved (solution became clear), and cooled to-10 ℃. The solution was kept at a temperature range of-10 to-5 ℃ and a mixture of 4,4' -bis (sulfonyl chloride) diphenyl ether (100 mmol) and anhydrous N-methyl-2-pyrrolidone (42.00 g), which had been dissolved, was added dropwise thereto over a half hour, and then stirring was continued for 1 hour while keeping the solution at a temperature of 0 to 5 ℃. The resulting reaction solution was slowly dripped into about 8 liters of water, and after settling and recovering precipitates by filtration and repeating the same procedure, washing with pure water was repeated 3 times to obtain a wet product. And dried in a vacuum oven at 80 ℃ for more than 24h to obtain the final product. The resulting random copolymer was named Polymer-7, which has the following structural formula. m and n are the respective numbers of repeating units, and the mole fractions of the structural units are m/(m + n) =0.5 and n/(m + n) =0.5, respectively.
(Polymer-7)
Figure PCTCN2020091094-APPB-000014
Synthesis examples 8 to 9:
synthesis methods of Polymer-8 and Polymer-9 with reference to Synthesis example 7, except that the molar fractions of the diamine monomers were adjusted to: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (75 mmol), 4,4 '-diaminodiphenyl ether (25 mmol) (synthesis example 8) and 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (25 mmol), 4,4' -diaminodiphenyl ether (75 mmol) (synthesis example 9). Other conditions/procedures were exactly the same as in Synthesis example 7. Thus, the chemical formulae of Polymer-8 and Polymer-9 are identical to Polymer-7, except that the molar fraction m/(m + n) is varied to 3:1 (Synthesis example 8: polymer-8) and 1:3 (Synthesis example 9: polymer-9).
Synthesis example 10:
in a four-necked flask with a mechanical stirrer, a thermometer and a high purity nitrogen atmosphere, 2,2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane (50 mmol), 4,4' -diaminodiphenyl ether (50 mmol), 2-methylpyridine (300 mmol) and anhydrous N-methyl-2-pyrrolidone (NMP) (47.25 g) were charged, stirred to be completely dissolved (the solution became clear), and cooled to-10 ℃. The solution was kept at a temperature range of-10 to-5 ℃ and a mixture of 4,4' -bis (sulfonyl chloride) diphenyl ether (100 mmol) and anhydrous N-methyl-2-pyrrolidone (42.00 g), which had been dissolved, was added dropwise thereto over a half hour, and then stirring was continued for 1 hour while keeping the solution at a temperature of 0 to 5 ℃. The resulting reaction solution was slowly dripped into about 8 liters of water, and after settling and recovering precipitates by filtration and repeating the same procedure, washing with pure water was repeated 3 times to obtain a wet product. And dried in a vacuum oven at 80 ℃ for more than 24h to obtain the final product. The resulting random copolymer was designated as Polymer-10 and its structural formula was as follows. m and n are the respective numbers of repeating units, and the mole fractions of the structural units are m/(m + n) =0.5 and n/(m + n) =0.5, respectively.
(Polymer-10)
Figure PCTCN2020091094-APPB-000015
Synthesis examples 11 to 12:
synthesis methods of Polymer-11 and Polymer-12 with reference to Synthesis example 10, except that the molar fractions of the diamine monomers were adjusted to: 2,2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane (75 mmol), 4,4 '-diaminodiphenyl ether (25 mmol) (Synthesis example 11) and 2,2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane (25 mmol), 4,4' -diaminodiphenyl ether (75 mmol) (Synthesis example 12). Other conditions/procedures were exactly the same as those in Synthesis example 10. Thus, the chemical formulae of Polymer-11 and Polymer-12 are identical to Polymer-10, except that the molar fraction m/(m + n) is varied to 3:1 (Synthesis example 11: polymer-11) and 1:3 (Synthesis example 12: polymer-12).
Synthesis example 13:
in a four-necked flask with mechanical stirrer, thermometer and high purity nitrogen atmosphere, 2,2' -bis (trifluoromethyl) diaminobiphenyl (50 mmol), 2,2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane (50 mmol), 2-methylpyridine (300 mmol) and anhydrous N-methyl-2-pyrrolidone (NMP) (47.25 g) were charged, stirred until completely dissolved (solution became clear), and cooled to-10 ℃. The solution was kept at a temperature range of-10 to-5 ℃ and a mixture of 4,4' -bis (sulfonyl chloride) diphenyl ether (100 mmol) and anhydrous N-methyl-2-pyrrolidone (42.00 g), which had been dissolved, was added dropwise thereto over a half hour, and then stirring was continued for 1 hour while keeping the solution at a temperature of 0 to 5 ℃. The resulting reaction solution was slowly dripped into about 8 liters of water, and after settling and filtering to recover precipitates and repeating the same process, washing with pure water was repeated 3 times to obtain a wet product. And dried in a vacuum oven at 80 ℃ for more than 24h to obtain the final product. The resulting random copolymer was designated as Polymer-13 and its structural formula was as follows. m and n are the respective numbers of repeating units, and the mole fractions of the structural units are m/(m + n) =0.5 and n/(m + n) =0.5, respectively.
(Polymer-13)
Figure PCTCN2020091094-APPB-000016
Synthesis examples 14 to 15:
synthesis methods of Polymer-14 and Polymer-15 with reference to Synthesis example 13, except that the molar fractions of the diamine monomers were adjusted to: 2,2 '-bis (trifluoromethyl) diaminobiphenyl (75 mmol), 2,2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane (25 mmol) (FIG. 14) and 2,2' -bis (trifluoromethyl) diaminobiphenyl (25 mmol), 2,2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane (75 mmol) (FIG. 15). Other conditions/procedures were exactly the same as in Synthesis example 13. Thus, the chemical formulae of Polymer-14 and Polymer-15 are identical to Polymer-13, except that the molar fraction m/(m + n) is varied to be 3:1 (Synthesis example 14: polymer-14) and 1:3 (Synthesis example 15: polymer-15).
Synthesis example 16:
in a four-necked flask with a mechanical stirrer, a thermometer and a high purity nitrogen atmosphere, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (50 mmol), 2,2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane (50 mmol), 2-methylpyridine (300 mmol) and anhydrous N-methyl-2-pyrrolidone (NMP) (47.25 g) were charged, stirred to complete dissolution (solution becomes clear), and cooled to-10 ℃. The solution was kept at a temperature range of-10 to-5 ℃ and a mixture of 4,4' -bis (sulfonyl chloride) diphenyl ether (100 mmol) and anhydrous N-methyl-2-pyrrolidone (42.00 g), which had been dissolved, was added dropwise thereto over a half hour, and then stirring was continued for 1 hour while keeping the solution at a temperature of 0 to 5 ℃. The resulting reaction solution was slowly dripped into about 8 liters of water, and after settling and recovering precipitates by filtration and repeating the same procedure, washing with pure water was repeated 3 times to obtain a wet product. And dried in a vacuum oven at 80 ℃ for more than 24h to obtain the final product. The resulting random copolymer was designated as Polymer-16 and its structural formula was as follows. m and n are the respective numbers of repeating units, and the mole fractions of the structural units are m/(m + n) =0.5 and n/(m + n) =0.5, respectively.
(Polymer-16)
Figure PCTCN2020091094-APPB-000017
Synthesis examples 17 to 18:
synthesis methods of Polymer-17 and Polymer-18 with reference to Synthesis example 16, except that the molar fractions of diamine monomers were adjusted to: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (75 mmol), 2,2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane (25 mmol) (Synthesis example 17) and 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (25 mmol), 2,2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane (75 mmol) (Synthesis example 18). Other conditions/procedures were exactly the same as those in Synthesis example 16. Thus, the chemical formulae of Polymer-17 and Polymer-18 are identical to Polymer-16, except that the molar fraction m/(m + n) is varied to be 3:1 (Synthesis example 17: polymer-17) and 1:3 (Synthesis example 18: polymer-18).
Synthesis example 19:
in a four-necked flask equipped with a mechanical stirrer, a thermometer and a high purity nitrogen atmosphere, p-phenylenediamine (50 mmol), 4,4' -diaminodiphenyl ether (50 mmol), 2-methylpyridine (300 mmol) and anhydrous N-methyl-2-pyrrolidone (NMP) (47.25 g) were charged, stirred until completely dissolved (solution became clear), and cooled to-10 ℃. The solution was kept at a temperature range of-10 to-5 ℃ and a mixture of 4,4' -bis (sulfonyl chloride) diphenyl ether (100 mmol) and anhydrous N-methyl-2-pyrrolidone (42.00 g), which had been dissolved, was added dropwise thereto over a half hour, and then stirring was continued for 1 hour while keeping the solution at a temperature of 0 to 5 ℃. The resulting reaction solution was slowly dripped into about 8 liters of water, and after settling and filtering to recover precipitates and repeating the same process, washing with pure water was repeated 3 times to obtain a wet product. And dried in a vacuum oven at 80 ℃ for more than 24h to obtain the final product. The resulting random copolymer was designated as Polymer-19 and its structural formula was as follows. m and n are the respective numbers of repeating units, and the mole fractions of the structural units are m/(m + n) =0.5 and n/(m + n) =0.5, respectively.
(Polymer-19)
Figure PCTCN2020091094-APPB-000018
Synthesis examples 20 to 21:
synthesis methods of Polymer-20 and Polymer-21 with reference to Synthesis example 19, except that the molar fractions of the diamine monomers were adjusted to: p-phenylenediamine (75 mmol), 4,4 '-diaminodiphenyl ether (25 mmol) (Synthesis example 20), and p-phenylenediamine (25 mmol), 4,4' -diaminodiphenyl ether (75 mmol) (Synthesis example 21). Other conditions/procedures were exactly the same as in Synthesis example 19. Thus, the chemical formulae of Polymer-20 and Polymer-21 are identical to Polymer-19, except that the molar fraction m/(m + n) is varied to 3:1 (Synthesis example 20: polymer-20) and 1:3 (Synthesis example 21: polymer-21).
Synthesis examples 22 to 25 are not mixed polymers, but are included in the claims of the present invention. X1 and X2 represented in the general formula (1) of the component (A) according to claim 1 may be the same or different divalent aromatic linking groups. When X1 and X2 are the same aromatic linking group, the following polymers 22 to 25 (structural formula shown below) can still be synthesized by the method of the aforementioned Synthesis example 1. Except that the 2,2 '-bis (trifluoromethyl) diaminobiphenyl (50 mmol) and 4,4' -diaminodiphenyl ether (50 mmol) components in synthesis example 1 were replaced by the following compounds, respectively: 2,2' -bis (trifluoromethyl) diaminobiphenyl (100 mmol) (synthesis example 22: polymer-22); 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (100 mmol) (Synthesis example 23: polymer-23); 2,2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane (100 mmol) (synthesis 24: polymer-24); 4,4' -diaminodiphenyl ether (100 mmol) (synthesis example 25: polymer-25).
Synthesis example 22:
(Polymer-22)
Figure PCTCN2020091094-APPB-000019
Synthesis example 23:
(Polymer-23)
Figure PCTCN2020091094-APPB-000020
Synthesis example 24
(Polymer-24)
Figure PCTCN2020091094-APPB-000021
Synthesis example 25:
(Polymer-25)
Figure PCTCN2020091094-APPB-000022
Embodiments of the negative photosensitive composition, the method for producing a pattern cured product, the redistribution layer, the interlayer insulating buffer film, the coverlay or the surface protective film, and the electronic device according to the present invention will be described in detail below. The present invention is not limited to the following embodiments. In the present specification, "a or" B "may include either one of a and B, or both of them. The numerical range represented by the term "to" means a range including the numerical values described before and after the term "to" as the minimum value and the maximum value, respectively.
The negative photosensitive composition of the present invention contains at least (A) a polysulfonamide polymer (having a structure represented by general formula (1)), (B) a photoacid generator, (C) a crosslinking agent, and (D) a solvent. The ingredients used in the compositions of the present invention are described in detail below, wherein the polysulfonamide polymers, properties and synthesis of component A are described in the first section above.
2. (B): photoacid generators
The photoacid generator as the component (B) in the present invention is a compound that generates an acid upon irradiation with light. The negative-type photosensitive composition containing a polysulfonamide polymer herein, after film formation, generates photoacid upon exposure which causes crosslinking of the polymer in the film to significantly reduce the solubility of the exposed portion. In the non-exposed portions, these photoacid generators do not chemically react and thus maintain good solubility in the developer. Thus, there is a large difference (contrast) in the dissolution rates of the exposed and non-exposed areas (dark areas), and a film having a microstructured relief pattern is obtained after the development step.
The photoacid generator is selected from, but not limited to, ionic compounds including sulfonium, phosphonium, or iodonium salts; the nonionic compound includes an oxime sulfonate, a sulfonate compound, or a quinone diazide compound; or mixtures thereof. From the viewpoint of sensitivity and imaging property, oxime sulfonate compounds are preferable. Oxime sulfonic acid ester compounds are photoacid compounds having excellent sensitivity to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a general ultraviolet mercury lamp. Many oxime sulfonate compounds are commercially available. The following formula (9) represents several common oxime ester compounds.
Figure PCTCN2020091094-APPB-000023
The content of the oxime ester compound is preferably 0.1 to 20 parts by mass, more preferably 1.0 to 10.0 parts by mass, per 100 parts by mass of the component (a) in order to obtain an optimum resolution and to improve a pattern contrast. Within the above range, the exposed portion of the polymer may be crosslinked to a good degree to give a practical relief pattern. Here, the component (B) may be used alone or in combination of two or more
3. (C): crosslinker component
The crosslinking agent component (C) in the photosensitive polysulfonamide composition of the present invention is a compound capable of crosslinking reaction with the polysulfonamide polymer of component (a) in the step of exposing and heat-curing the negative photosensitive composition. Due to the fact thatThese effective crosslinking reactions result in cured films from polysulfonamide polymers having excellent photosensitive resolution and good adhesion, mechanical properties, and chemical resistance at relatively low post-cure temperatures (typically 250 ℃ C.) and thus avoid the use of high post-cure temperatures in the process flow. The crosslinking agent preferably contains at least one compound having-CH-group in view of the mechanical properties of the cured film and the crosslinkability at the time of curing at low temperature 2 Alkoxy/hydroxy compounds of OR (R is a hydrogen atom OR a 1-valent organic group); an epoxy compound; an oxetane compound or a vinyl ether compound. From the viewpoint of high mechanical properties of the cured film and high reactivity at the time of curing at low temperature, a compound represented by the following formula (10) having a hydroxyalkyl group such as a hydroxyl group or a hydroxymethyl group or an alkoxyalkyl group such as an alkoxymethyl group is preferable.
Figure PCTCN2020091094-APPB-000024
The content of the crosslinking agent (C) is preferably 2 to 50 parts by mass, and more preferably 8 to 40 parts by mass, per 100 parts by mass of the component (a), in order to obtain an optimum effect of chemical agent corrosion resistance. If the amount of the crosslinking agent is less than 2 parts by mass, the crosslinking and the improvement of the chemical resistance are not remarkably attained; if the crosslinking agent is more than 50 parts by mass, various mechanical properties of the material may be degraded. The component (C) may be used singly or in combination of two or more of the above crosslinking agents.
4. (D) component (A): solvent(s)
(D) Component (C) as a solvent, and the varnish is formed by dissolving the above components (a) to (C). (D) Ingredients may be used including at least one compound selected from the following solvents: esters, ethers, ether-esters, ketones, ketone-esters, aromatics, and/or halogenated hydrocarbon solvents. In general, there is no particular limitation as long as it can sufficiently dissolve other components in the negative-type photosensitive composition and is suitable for the photolithography process. Some common solvents include N-methyl-2-pyrrolidone, gamma-butyrolactone, epsilon-caprolactone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, 2-methoxyethanol, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butanediol acetate, 1,3-butanediol acetate, cyclohexanone, tetrahydrofuran, and the like. Among these solvents, a solvent system mainly composed of γ -butyrolactone, N-methyl-2-pyrrolidone, and cyclopentanone is preferably used from the viewpoint of excellent solubility and coatability of the resin film.
(D) The content of the component (A) is not particularly limited, but is preferably 50 to 800 parts by mass, more preferably 60 to 300 parts by mass, and still more preferably 80 to 220 parts by mass, based on 100 parts by mass of the component (A), from the viewpoint of controlling the film thickness mainly
5. Other ingredients of the composition
The resin composition of the present invention may contain, in addition to the above-mentioned components (a) to (D), other components such as an anticorrosive agent, a thickener, a softener, a dissolution accelerator, a leveling agent, and the like as required. The principle of adding these additives is not to substantially impair the basic properties of the final cured film of the present invention. Often these components improve certain properties of the material making it more suitable for some customer-specific processes and applications. These components and effects are described in detail below.
Corrosion inhibitor-when the photosensitive resin composition of the present invention is applied to copper or a copper alloy substrate, at least one compound containing a triazole ring, an imidazole ring and a thiazole ring skeleton represented by the general formula (11) containing a carbon atom and a nitrogen atom may be added to the composition in order to suppress discoloration and decrease in stability due to corrosion of copper. Examples of the azole compound include 1H-triazole, 1H-benzotriazole, 2- (2H-benzotriazol-2-yl) p-cresol, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [ 2-hydroxy-3,5-bis (. Alpha., α -dimethylbenzyl) phenyl ] -benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2 '-hydroxy-5' -t-octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, and the like. Benzotriazole compounds containing a benzene ring such as tolyltriazole, 5-methyl-1H-benzotriazole, or a mixture of 1 or more thereof are preferred.
Figure PCTCN2020091094-APPB-000025
The content of the corrosion inhibitor is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, per 100 parts by mass of the component (a) in order to obtain an optimum effect of inhibiting metal corrosion.
Thickener-in order to improve the adhesion between a cured film made of the photosensitive resin composition of the present invention and a substrate, a thickener component may be blended in the photosensitive resin composition. The tackifier may be selected from organic silane compounds and aluminum-based adhesion promoters including tris (ethylacetoacetato) aluminum, tris (acetylacetonate) aluminum, ethylacetoacetate diisopropylester, and the like. In order to improve the adhesion to a substrate such as copper, an organic silane compound is preferably used. The organosilane compound includes: 3- (2,3-glycidoxy) propyltrimethoxysilane, 3- [ bis (2-hydroxyethyl) amino ] propane-triethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-acryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, triethoxysilylpropylethyl carbamate, 3- (triethoxysilyl) propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. These organic silane compounds can be used alone, can also be combined with 2 or more. The content of the thickener component in the composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, per 100 parts by mass of the component (a), from the viewpoint of improving the adhesion line to the substrate.
Softeners-in the negative-type polysulfonamide compositions herein, the softeners may increase the flexibility of the cured film made therefrom to increase the elongation parameter at break of the material. As the softener, compounds such as polyols, polyesters, polyhydroxy esters, etc. having different molecular weights can be selected. These softeners may be used alone or in combination of two or more. If a softener component is selected, the content thereof in the composition is preferably 1 to 40 parts by mass per 100 parts by mass of the component (A).
Dissolution accelerators-in the negative-type polysulfonamide compositions herein, the dissolution accelerators may increase the rate of dissolution of the unexposed portions to increase the resolution and development contrast of the micropattern. Examples of the dissolution accelerator include compounds having a hydroxyl group or a carboxyl group. Examples of the compound having a hydroxyl group include p-cumylphenol, resorcinols, bisphenols, other linear or non-linear phenolic compounds, phenolic substitutes of 2 to 5 for diphenylmethane, and phenolic substitutes of 1 to 5 for 3,3-diphenylpropane. These dissolution promoters may be used alone or in combination of two or more. The content of the dissolution promoter component in the composition is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (a).
Leveling agent-in order to improve coatability and surface smoothness when a film is formed by spin coating, a surfactant may be added to the composition as a leveling agent, and examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. Some examples directly available from the market include MegafacF171, F173 (manufactured by japan ink chemical industries); KP341, KBM303, and KBM803 of organosiloxane (manufactured by shin-Etsu chemical Co., ltd.); there are also fluorine-containing surfactants PolyFox PF-6320 (Omnova Solutions), fluorad FC430, FC171 (manufactured by Sumitomo 3M Co., ltd.), and the like. The content of the surfactant used is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the component (a).
The following are preferred embodiments of negative-working photosensitive compositions containing polysulfonamide polymers of the present invention.
Example 1: the photosensitive negative-type resin composition of the present invention was obtained by dissolving polymer-1 (100 parts by mass) obtained in synthesis example 1, B-1 (3 parts by mass, relative to polymer-1) as a photoacid, and C-1 (20 parts by mass) as a crosslinking agent in cyclopentanone (D-1, 180 parts), and adding E-1 (1.5 parts by mass) as an anticorrosive agent, F-1 (2 parts by mass) as a thickener, and H-1 (0.05 parts by mass) as a leveling agent. The information on the other components than the polymer component (A) is referred to below:
Figure PCTCN2020091094-APPB-000026
(D-1) cyclopentanone
(D-2) 90% cyclopentanone/10% methyl amyl ketone
(E-1): 1H-benzotriazole
(E-2) 2- (2H-benzotriazol-2-yl) p-cresol
(E-3) 5-methyl-1H-benzotriazole
(F-1):Z-6040 Silane(Dow Corning)
(F-2) 3- (2,3-glycidoxy) propyltrimethoxysilane
(F-3): 3- [ bis (2-hydroxyethyl) amino ] propane-triethoxysilane
(G-1) (softener) K-PURE CDR-3314 (King Industries, inc)
(H-1) (leveling agent) PolyFox PF-6320 (OMNOVA Solutions Inc.)
Examples 2 to 25 and comparative examples 1 to 5 were prepared in exactly the same manner as in example 1 except that each component or content thereof was different. The composition components described in these examples/comparative examples and the contents (parts by mass in parentheses) of the respective components thereof with respect to the polymer (A) (100 parts by mass) are shown in Table-1 below.
TABLE-1
Figure PCTCN2020091094-APPB-000027
Figure PCTCN2020091094-APPB-000028
NA: representing compositions without such components.
The photosensitive resin compositions (also called varnishes) obtained in the above examples/comparative examples were filtered through a polytetrafluoroethylene filter membrane to obtain final negative photosensitive resin compositions. Depending on the polymer concentration in the composition and the viscosity of the varnish, a polytetrafluoroethylene filter membrane with a pore size of 0.45-3 microns can be chosen.
The varnish is then formed into a polysulfonamide resin film of about 10 μm thickness for coating on a substrate material by the method of claim 6. These polysulfonamide resin films and cured product films having a relief pattern produced therefrom will be further described below.
The method for preparing a pattern cured product by using the polysulfonamide composition comprises the following steps:
(a) Resin film forming step: a step of applying the polysulfonamide polymer composition described in claims 1 to 5 onto a substrate, and heating and drying the composition to remove the solvent to form a photosensitive resin film. Examples of the substrate include a semiconductor substrate such as an Si substrate (silicon wafer), a ceramic substrate, a metal substrate (including a copper substrate, an aluminum substrate, a copper alloy substrate, and the like), a silicon nitride substrate, and the like. The coating method may be spin coating, spray coating, dipping, or the like, and spin coating by a spin coater is preferred from the viewpoint of controlling the film thickness. The heat drying may be performed using a hot plate, an oven, or the like. The heating and drying temperature is preferably 90 to 150 ℃, more preferably 90 to 130 ℃. The film thickness of the resin film is preferably 1 to 50 μm, and more preferably 1 to 30 μm.
(b) An exposure step: and pattern-exposing the photosensitive resin film using a mask. The pattern exposure is, for example, exposure to a predetermined pattern through a photomask. The active light to be irradiated includes ultraviolet rays such as i-rays, visible rays, and radiation rays, and i-rays are preferable. As the exposure apparatus, a scanner exposure machine, a projector exposure machine, a stepper exposure machine, or the like can be used.
(c) A developing step: by performing the developing step, a resin film having a microstructure relief pattern can be obtained. Generally, development is performed by a method such as a dipping method or a spin spray method. In the case of using the negative photosensitive resin composition of the present invention, the developer can remove the unexposed portion of the film to obtain a relief pattern. The developing time is generally 10 seconds to 15 minutes, and preferably 20 seconds to 5 minutes from the viewpoint of improving productivity and process control. As the developer, inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia water; organic amines such as ethylamine, triethanolamine and diethylamine may also be used; an aqueous solution of quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH) and tetrabutylammonium hydroxide may also be used. In the above-mentioned various developing solutions, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount as required to enhance the effect. Among these developers, an aqueous tetramethylammonium hydroxide solution is preferable. In general, an aqueous solution of TMAH with a concentration of 2.38% is preferably used. Note that, depending on the dissolution rate of the (a) component, the concentration of TMAH in the alkaline developer may be diluted as appropriate to adjust the film dissolution rates of the exposed and non-exposed regions so as to obtain an optimum contrast ratio upon development. After the development, the developer may be removed by washing with a rinse solution, whereby a patterned thin film can be obtained. The rinse solution may be distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, or the like, used alone or in combination.
(d) And a heat curing step, wherein the heat treatment step is a process of performing heat curing on the relief pattern resin film so as to obtain the optimal physical properties of the material. In this step, the relief pattern obtained by the above-described development is heated to be converted into a cured relief pattern. A hot plate or an oven may be used, and the heating temperature is preferably 250 ℃ or lower, more preferably 180 to 230 ℃. The time of the heat treatment is usually 30 minutes to 4 hours, and more preferably 30 minutes to 2 hours, from the viewpoint of the time required for the crosslinking reaction. The atmosphere of the heat treatment may be air or an inert gas atmosphere such as nitrogen or argon. From the viewpoint of preventing oxidation of the pattern resin film and cost, it is preferable to heat-cure the pattern resin film in an atmosphere of high-purity nitrogen gas (. Gtoreq.99.999%).
The cured product of the present invention is a cured polymer resin film obtained by the above-described treatment step, and such a film may be a cured film having a relief pattern as described above or a cured film having no pattern.
The cured film may be stacked in the semiconductor element in direct contact with the semiconductor element, or may be stacked with another layer interposed therebetween. They may also be used to encase other materials such as metal wires to act as an insulating medium. Exemplary applications include redistribution layers, interlayer insulating buffer films, covercoat or surface protection film materials, and the like.
An example of a method of manufacturing a redistribution layer according to the present invention will be described with reference to fig. 1.
Figure 1 (schematic representation of a cross-section of a structure) is a construction of a redistribution layer structure using the composition of the present invention and embodiments thereof. It should be noted that the film thickness and device size ratios in the figures do not represent true ratios. In the present embodiment, by the design of the two-layer wiring structure, a signal can be input/output between the chip (Al Pad: aluminum contact Pad electrode) and the outside (Solder Bump: solder ball). The two-layer wiring structure is realized by copper redistribution layer leads (Cu RDL) wrapped on polymer layers (polymer layer 1 and polymer layer 2) of insulating material. As shown, copper leads connect the aluminum sheet contact plate electrodes (Al pads) and Solder balls (Solder Bump) on the chip. The solder balls are connected to other packages or motherboards in the next process after packaging, so that the package-to-package or package-to-motherboard connection is realized. The connection of the solder ball and the copper lead is realized by an under bump metallurgy (UBM Stud). These two layers of insulating materials (polymer layer 1 and polymer layer 2) employ the polysulfonamide cured film of the present invention. The purpose of rewiring and changing the position/size of the contact electrode can be realized through the design and the construction. The polysulfonamide cured film herein functions not only as an insulating dielectric material for covering the copper lead but also as a structural member for relaxing internal stress. These materials need to have good long term stability to maintain good stability and material recovery during thermal expansion and contraction cycles with changing temperatures and the accompanying stress changes.
By using one or more materials selected from the redistribution layer, the interlayer insulating buffer film, the coverlay film, and the surface protective film, it is possible to manufacture an electronic device such as a semiconductor device and a multilayer wiring board having high reliability and high stability.
8. Evaluation of adhesion
The cured film is mainly used as an insulating material for wrapping the copper wire, so that the good adhesion between the two materials is a critical material parameter. According to one standard adherence test method of the American Society for Testing and Materials (ASTM): d3359 Standard method for testing pasting lines with adhesive Tape (Standard Test method for Measuring Adhesion by Tape Test), the resulting cured film was cut into 10X 10 grid-like small cells (1 mm. About.1 mm per cell area) in the vertical direction with a saw-tooth grid blade. Adhesive tapes (3M) were attached to these small pieces of the cured film according to the method described in ASTM D3359, and the adhesive tapes were peeled off. The line of application of the material was judged from the number of small pieces of the cured film peeled from the substrate when the adhesive tape was peeled off. In the present invention, the following criteria a or B are used to judge the adhesiveness of the material film to the copper substrate. The detailed results are shown in Table-2.
A: lattice without peeling
B, the number of the peeling lattices is at least 1
As seen from the following Table-2, the polysulfonamide cured films obtained by the present invention have excellent adhesion to copper substrates as a whole.
9. Evaluation of discoloration inhibition
With respect to the resulting cured film coated on copper metal, the appearance was evaluated by an optical microscope and naked eyes. If the cured film can well maintain the original color of the underlying copper metal film after curing, it is evaluated as A that discoloration is suppressed; if the color of copper under the cured film was clearly shifted to deep red/brown, it was evaluated as B that discoloration was not suppressed. The detailed results are shown in Table-2 below.
A: inhibit color change
B: without inhibiting discoloration
As can be seen from the following Table-2, the polysulfonamide cured films obtained by the present invention generally have a good protective effect on copper substrates and inhibit the discoloration of copper metal.
In conclusion, the polysulfonamide cured material film provided by the invention effectively overcomes the defect that the adhesion of the materials to copper substrate materials is not strong, and plays a good role in protecting the copper metal of the substrate.
TABLE-2
Examples/comparative examples Adhesion Property Discoloration inhibition
Example #1 A A
Example #2 A A
Example #3 A A
Example #4 A A
Example #5 A B
Example #6 B A
Example #7 A A
Example #8 B B
Example #9 A A
Example #10 A A
Example #11 B B
Example #12 A A
Example #13 A A
Example #14 A A
Example #15 A A
Example #16 A A
Example #17 A A
Example #18 A B
Example #19 A A
Example #20 A A
Example #21 A A
Example #22 A A
Example #23 A A
Example #24 A A
Example #25 A A
Comparative example #1 Can not form a film Can not form a film
Comparative example #2 Can not form a film Fail to form a film
Comparative example #3 A A
Comparative example #4 A B
Comparative example #5 B B
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

  1. A polysulfonamide polymer having the general formula (1),
    Figure PCTCN2020091094-APPB-100001
    the polysulfonamide polymer has a repeating unit structural formula as follows, wherein m and n represent the number of structural units in the polymer and are integers of 1-99.
  2. The polysulfonamide polymer according to claim 1 wherein X1 and X2 in formula (1) are divalent aromatic linking groups which may be different or the same and have a group represented by the following formula (2), (3) or (4);
    Figure PCTCN2020091094-APPB-100002
    wherein R is 1 ，R 2 ，R 3 ，R 4 Each represents a hydrogen atom or a monovalent organic group;
    Figure PCTCN2020091094-APPB-100003
    wherein Q is a direct bond or a divalent organic group selected from O, S,CO、 SO 2 、Si(CH 3 ) 2 、CH(OH)、(CH 2 ) p (1≤p≤10)、(CF 2 ) q (1≤q≤10)、C(CH 3 ) 2 、C(CF 3 ) 2 Substituted or unsubstituted-o, -m, -p-phenylene;
    Figure PCTCN2020091094-APPB-100004
    wherein T is a direct bond or a divalent organic group selected from O, S, CO, SO 2 、Si(CH 3 ) 2 、CH(OH)、(CH 2 ) p (1≤p≤10)、(CF 2 ) q (1≤q≤10)、C(CH 3 ) 2 、C(CF 3 ) 2 Substituted or unsubstituted-o, -m, -p-phenylene, wherein R 5 ～R 12 Are identical or different monovalent organic radicals selected from the group consisting of H, CH 3 Or CF 3 ；
    Wherein Y in the polysulfonamide polymer of the general formula (1) is a divalent aromatic group selected from the structural units represented by the following formula (5) or (6):
    Figure PCTCN2020091094-APPB-100005
    wherein U in the general formula (6) is a direct bond or a divalent organic group selected from O, S, CO, SO 2 、Si(CH 3 ) 2 、CH(OH)、(CH 2 ) p (1≤p≤10)、(CF 2 ) q (1≤q≤10)、C(CH 3 ) 2 、C(CF 3 ) 2 Substituted or unsubstituted-o, -m, -p-phenylene.
  3. The polysulfonamide polymer of claim 1 which is a block copolymer or a random copolymer having a weight average molecular weight in the range of 5,000 to 200,000.
  4. A negative-tone photosensitive composition containing the polysulfonamide polymers of any of claims 1-3 comprising:
    (A) A polysulfonamide polymer;
    (B) Photoacid generators: the content thereof in the composition is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the component (a);
    (C) A crosslinking agent: the content thereof in the composition is preferably 2 to 50 parts by mass, more preferably 8 to 40 parts by mass, relative to 100 parts by mass of the component (a);
    (D) Solvent: the content thereof in the composition is preferably 50 to 800 parts by mass, more preferably 60 to 300 parts by mass, and still more preferably 80 to 220 parts by mass, based on 100 parts by mass of the component (a).
  5. The negative-type photosensitive composition containing a polysulfonamide containing polymer according to claim 4 wherein component (B) is at least one photoacid generator. The photoacid generator is selected from, but not limited to, ionic compounds including sulfonium, phosphonium, or iodonium salts; the nonionic compound includes an oxime sulfonate, a sulfonate compound, or a quinone diazide compound; or mixtures thereof. From the viewpoint of sensitivity and imaging property, oxime sulfonate compounds are preferable; and/or
    Wherein the component (C) contains at least one compound having a-CH 2 Alkoxy compounds/hydroxy compounds of OR (R is a hydrogen atom OR a 1-valent organic group); an epoxy compound; oxetane compounds and vinyl ether compounds, preferably compounds having an alkoxyalkyl group such as a hydroxymethyl group or an alkoxymethyl group; and/or
    Wherein the ingredients of said composition are dissolved in a solvent (D) comprising at least one compound selected from the group consisting of: esters, ethers, ether-esters, ketones, ketone-esters, aromatics, and/or halogenated hydrocarbon solvents.
  6. A negative-type photosensitive composition containing polysulfonamide polymers as defined in any of claims 4 to 5, which is prepared by a method comprising the steps of:
    (a) A step of coating the polysulfonamide polymer composition on a substrate and heating to remove the solvent to form a photosensitive resin film;
    (b) A step of pattern-exposing the photosensitive resin film by using a mask;
    (c) A step of removing the unexposed area of the coating layer to obtain a resin cured film having a relief pattern, and
    (d) And a step of subjecting the relief pattern resin film to a heat curing treatment.
  7. The cured product having a relief pattern according to claim 6, wherein the temperature of the heat treatment is 250 ℃ or less.
  8. The embossed patterned cured product according to claim 6, which is a cured product film having a microstructured embossed pattern.
  9. The cured product having a relief pattern according to any one of claims 6 to 8 is applied to a redistribution layer, an interlayer insulating buffer film, a covercoat layer, or a surface protective film.
  10. An electronic device comprising the redistribution layer, the interlayer insulating buffer film, the covercoat layer, or the surface protective film of claim 9.
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