CN115551923A - Polysulfonamide polymers, positive photosensitive compositions containing them and their use - Google Patents

Polysulfonamide polymers, positive photosensitive compositions containing them and their use Download PDF

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CN115551923A
CN115551923A CN202080100662.XA CN202080100662A CN115551923A CN 115551923 A CN115551923 A CN 115551923A CN 202080100662 A CN202080100662 A CN 202080100662A CN 115551923 A CN115551923 A CN 115551923A
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崔庆洲
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Abstract

The invention discloses a polysulfonamide polymer, a positive photosensitive composition containing the polysulfonamide polymer and application of the positive photosensitive composition. The positive photosensitive composition containing the polysulfonamide polymer comprises the following raw materials in percentage by weight: polysulfonamide polymers, photoacid generators, crosslinkers, corrosion inhibitors, adhesion promoters, and solvents. 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, positive photosensitive compositions containing them and their use Technical Field
The invention relates to a photosensitive dielectric material applied in the field of semiconductors, in particular to a positive photosensitive composition containing a polysulfonamide polymer, a cured product prepared from the positive photosensitive composition and application of the positive 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. The redistribution layer material is 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, paste performance, 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), polybenzoxazole (PBO), benzocyclobutene (BCB) and the like have gradually become mainstream materials in this field due to their excellent high-temperature-resistant material properties. In addition, the new high-performance insulating material has great application prospect in other applications such as interlayer insulating buffer films, covering coatings or surface protection films.
The existing advanced packaging technology process generally combines the adoption of alkylene oxide type EMC (Epoxy Molding Compounds) material and utilizes a lead-free welding material with a lower melting point (the melting point is approximately equal to 260 ℃ or lower) as a part of the process flow, which requires that the subsequent treatment process step cannot adopt higher post-curing temperature but requires that the material has better long-term stability. The traditional photosensitive polyimide, polybenzoxazole and benzocyclobutene usually require post-curing temperature of more than or equal to 300 ℃, so that the materials have great 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 purpose of the present invention is to overcome the defects of the existing photosensitive dielectric material, and to provide a new polysulfonamide polymer mainly used for positive photosensitive dielectric materials, 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 positive photosensitive compositions containing polysulfonamide polymers, which can provide effective crosslinking ability and excellent lithographic performance under a low-temperature (250 ℃ or lower) heat treatment condition, thereby providing cured products having relief microstructures.
Another object of the present invention is to provide a pattern cured product prepared from the above novel photosensitive polysulfonamide polymer composition.
It is still another object of the present invention to provide a use of the pattern 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 PCTCN2020091095-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 purpose of the invention and the technical problem to be solved can be further realized by adopting the following technical measures.
In the polysulfonamide polymer, 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 PCTCN2020091095-APPB-000002
wherein R is 1 ，R 2 ，R 3 ，R 4 Each represents a hydrogen atom or a monovalent organic group;
Figure PCTCN2020091095-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 PCTCN2020091095-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, in which R is 5 ～R 12 Are identical or different monovalent organic radicals selected from 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 group consisting of structural units represented by the following formula (5) or (6):
Figure PCTCN2020091095-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. The positive photosensitive composition containing a polysulfonamide polymer according to the present invention comprises:
(A) A polysulfonamide polymer;
(B) Photoacid generators: the content thereof in the composition is preferably 2 to 40 parts by mass, more preferably 8 to 30 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 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, relative to 100 parts by mass of the component (a);
(D) Corrosion inhibitor: the content thereof in the composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the component (a);
(E) Tackifier: the content thereof in the composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, relative to 100 parts by mass of the component (a); and
(F) 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, relative to 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 positive photosensitive composition containing polysulfonamide polymers described above contains component (B) which is at least one photoacid generator selected from one or more of quinone diazide compounds, sulfonate compounds, or triphenylsulfonium salt compounds; 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-based compounds, preferably compounds having an alkoxyalkyl group such as a hydroxymethyl group or an alkoxymethyl group; and/or
Wherein the component (D) is at least one compound having a triazole ring, an imidazole ring and a thiazole ring skeleton, which contains a carbon atom and a nitrogen atom; and/or
Wherein the component (E) is at least one of an organosilane compound-containing or aluminum-based adhesion promoter; and/or
Wherein the components of said composition are dissolved in a solvent (F) 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. The positive photosensitive composition containing polysulfonamide polymers provided by the invention can be used for preparing a cured product with a relief pattern, and is prepared by a method comprising the following steps:
(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 exposed region of the coating layer to thereby obtain a resin cured film having a relief pattern, and
(d) And a step of performing heat curing treatment on the relief pattern resin film.
The object of the present invention and the technical problems solved thereby can be further achieved by 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 cover coat or the surface protection film.
Compared with the prior art, the invention has obvious advantages and beneficial effects. As can be seen from the above technical solutions, in order to achieve the above object, the main technical contents of the present invention are as follows:
the invention provides a positive photosensitive composition containing a polysulfonamide polymer, a cured product prepared from the positive photosensitive composition and application of the cured product in semiconductor packaging,
as described above, the present invention discloses a polysulfonamide polymer, a positive photosensitive composition containing the polysulfonamide polymer, and applications thereof. The positive photosensitive composition containing the polysulfonamide polymer comprises the following raw materials in percentage by weight: polysulfonamide polymers, photoacid generators, crosslinkers, anti-corrosion agents, adhesion promoters, and solvents. 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.
By means of the technical scheme, the positive photosensitive composition containing the polysulfonamide polymer, the cured product prepared from the positive photosensitive composition and the application of the positive photosensitive composition in semiconductor packaging at least have 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 various monomers in the film, the components of the composition and the heat treatment conditions, the dissolution speed and the mechanical properties of the film and the properties of various other materials can be well regulated and optimized. In addition, the resin composition has excellent adhesion to various substrates even under conditions of curing at low temperatures. Finally, by using fluorine atom-containing monomers in the polymer synthesis process, the new materials can be remarkably improved in the aspect of reducing the water absorption of the materials, so that the cured material film prepared from the composition is 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 disclosed or used in the same kind of products, but rather are innovative, and it has great improvements in both formula and function, and has great technical progress, and produces good and practical effects, and has many enhanced effects compared with the existing products, so as to be more practical, and have industrial wide utility value, and it 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 present 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 polysulfonamide polymers, positive photosensitive compositions containing polysulfonamide polymers, cured products prepared therefrom, and their application in semiconductor packaging according to the present invention will be provided 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 various modifications can be made by those having ordinary knowledge in the art within the technical idea of the present invention.
1. (A) polysulfonamide polymers
The properties of the polysulfonamide polymers prepared in examples 1-25 are illustrated below.
Figure PCTCN2020091095-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 and have a group represented by the following general formula (2), (3) or (4).
Figure PCTCN2020091095-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 PCTCN2020091095-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 PCTCN2020091095-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 above polysulfonamide polymer, wherein Y in the general formula (1) is a divalent aromatic group selected from a structural unit represented by the following formula (5) or (6):
Figure PCTCN2020091095-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 sulfonyl chloride monomer (dissolved in the N-methylpyrrolidone) with the same molar amount as 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 carrying out vacuum drying at 80-120 ℃ to obtain the polysulfonamide polymer.
The polysulfonamide polymers described above 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 compound may be selected from monocarboxylic acids such as 3-carboxybenzenesulfonic acid and 4-carboxybenzenesulfonic acid and monoacid chloride compounds obtained by acid chlorination of their carboxyl groups, or may be selected from monocarboxylic acid compounds 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, or active ester compounds obtained by reaction of a monoacid chloride compound with N-hydroxybenzotriazole and N-hydroxy-5-norbornene-2, 3-dicarboxylimide. The blocking agent may be one or more of the compounds described above.
The polysulfonamide polymers described above are typically 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 judged by the time required for complete dissolution of the film.
In addition, the transmittance of 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 base polymer is preferably 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 warpage of the chip can be effectively inhibited after the film is cured and formed, so that the wafer reconstruction (wafer reconstruction) 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 PCTCN2020091095-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 equipped with a mechanical stirrer, a thermometer and a high purity nitrogen atmosphere, 2 '-bis (trifluoromethyl) diaminobiphenyl (50 mmol), 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 above solution was kept at a temperature ranging from-10 to-5 deg.C, and a mixed solution of dissolved 4,4' -bis (sulfonyl chloride) diphenyl ether (100 mmol) and anhydrous N-methyl-2-pyrrolidone (42.00 g) was added dropwise thereto over about half an hour, and then stirring was continued for 1 hour while keeping the solution at a temperature ranging from 0 to 5 deg.C. 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 PCTCN2020091095-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' -diaminodiphenyl ether (25 mmol) (Synthesis example 2), and 2,2 '-bis (trifluoromethyl) diaminobiphenyl (25 mmol), 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 '-bis (trifluoromethyl) diaminobiphenyl (47.5 mmol), 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 above solution was kept at a temperature ranging from-10 to-5 ℃ and a mixed solution of dissolved 4,4' -bis (sulfonyl chloride) diphenyl ether (100 mmol) and anhydrous N-methyl-2-pyrrolidone (42.00 g) was added dropwise thereto over a half hour, and then stirring was continued for 1 hour while keeping the solution at a temperature ranging from 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-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 PCTCN2020091095-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 diamine monomers were adjusted to: 2,2 '-bis (trifluoromethyl) diaminobiphenyl (71.25 mmol), 4' -diaminodiphenyl ether (23.75 mmol) (Synthesis example 5), 2 '-bis (trifluoromethyl) diaminobiphenyl (23.75 mmol), and 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 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-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (50 mmol), 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 (the solution became clear), and cooled to-10 ℃. The above solution was kept at a temperature ranging from-10 to-5 ℃ and a mixed solution of dissolved 4,4' -bis (sulfonyl chloride) diphenyl ether (100 mmol) and anhydrous N-methyl-2-pyrrolidone (42.00 g) was added dropwise thereto over a half hour, and then stirring was continued for 1 hour while keeping the solution at a temperature ranging from 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-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 PCTCN2020091095-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 diamine monomers were adjusted to: 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (75 mmol), 4 '-diaminodiphenyl ether (25 mmol) (Synthesis example 8), and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (25 mmol), 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 be 3:1 (Synthesis example 8: polymer-8) and 1:3 (Synthesis example 9: polymer-9).
Synthesis example 10:
in a four-neck flask with a mechanical stirrer, a thermometer and a high-purity nitrogen atmosphere, 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane (50 mmol), 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 (the solution became clear) and cooled to-10 ℃. The above solution was kept at a temperature ranging from-10 to-5 deg.C, and a mixed solution of dissolved 4,4' -bis (sulfonyl chloride) diphenyl ether (100 mmol) and anhydrous N-methyl-2-pyrrolidone (42.00 g) was added dropwise thereto over about half an hour, and then stirring was continued for 1 hour while keeping the solution at a temperature ranging from 0 to 5 deg.C. 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-10, 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-10)
Figure PCTCN2020091095-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, 3-hexafluoropropane (75 mmol) 4,4 '-diaminodiphenyl ether (25 mmol) (Synthesis example 11) and 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane (25 mmol), 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-neck flask with a mechanical stirrer, a thermometer and a high-purity nitrogen atmosphere, 2,2' -bis (trifluoromethyl) diaminobiphenyl (50 mmol), 2-bis [4- (4-aminophenoxy) phenyl ] -1, 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 above solution was kept at a temperature ranging from-10 to-5 ℃ and a mixed solution of dissolved 4,4' -bis (sulfonyl chloride) diphenyl ether (100 mmol) and anhydrous N-methyl-2-pyrrolidone (42.00 g) was added dropwise thereto over a half hour, and then stirring was continued for 1 hour while keeping the solution at a temperature ranging from 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-13, 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-13)
Figure PCTCN2020091095-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-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane (25 mmol) (Synthesis example 14) and 2,2' -bis (trifluoromethyl) diaminobiphenyl (25 mmol) 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane (75 mmol) (Synthesis example 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 equipped with a mechanical stirrer, a thermometer and a high purity nitrogen atmosphere, 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (50 mmol), 2-bis [4- (4-aminophenoxy) phenyl ] -1, 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 above solution was kept at a temperature ranging from-10 to-5 ℃ and a mixed solution of dissolved 4,4' -bis (sulfonyl chloride) diphenyl ether (100 mmol) and anhydrous N-methyl-2-pyrrolidone (42.00 g) was added dropwise thereto over a half hour, and then stirring was continued for 1 hour while keeping the solution at a temperature ranging from 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 PCTCN2020091095-APPB-000017
Synthesis examples 17 to 18:
synthesis methods of Polymer-17 and Polymer-18 reference synthesis example 16, except that the molar fractions of the diamine monomers were adjusted to: 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (75 mmol), 2-bis [4- (4-aminophenoxy) phenyl ] -1, 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, 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' -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 above solution was kept at a temperature ranging from-10 to-5 ℃ and a mixed solution of dissolved 4,4' -bis (sulfonyl chloride) diphenyl ether (100 mmol) and anhydrous N-methyl-2-pyrrolidone (42.00 g) was added dropwise thereto over a half hour, and then stirring was continued for 1 hour while keeping the solution at a temperature ranging from 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-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 PCTCN2020091095-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 '-diaminodiphenyl ether (25 mmol) (Synthesis example 20), p-phenylenediamine (25 mmol), and 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. If 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, 3-hexafluoropropane (100 mmol) (Synthesis example 24: polymer-24); 4,4' -diaminodiphenyl ether (100 mmol) (Synthesis example 25: polymer-25).
Synthesis example 22:
(Polymer-22)
Figure PCTCN2020091095-APPB-000019
Synthesis example 23:
(Polymer-23)
Figure PCTCN2020091095-APPB-000020
Synthesis example 24
(Polymer-24)
Figure PCTCN2020091095-APPB-000021
Synthesis example 25:
(Polymer-25)
Figure PCTCN2020091095-APPB-000022
Embodiments of the positive 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 recited before and after the term "to" as the minimum value and the maximum value, respectively.
The positive photosensitive composition of the present invention contains at least (A) a polysulfonamide polymer (the structure is represented by general formula (1)), (B) a photoacid generator, (C) a crosslinking agent, (D) an anticorrosive agent, (E) an adhesion promoter, and (F) a solvent. Hereinafter, each component used in the composition of the present invention will be described in detail. Wherein the component A polysulfonamide sulfonamide polymer, properties, and synthesis are as 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. In the positive photosensitive composition containing a polysulfonamide polymer herein, the photoacid generated by exposure increases the solubility of the exposed portion in an aqueous alkaline solution. These photoacid generators do not chemically react and function to inhibit dissolution in the unexposed portions. 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. Examples of photoacid commonly used in a positive photosensitive composition containing a polysulfonamide polymer include quinonediazide sulfonyl chloride compounds, onium salts such as diaryliodonium salts, triarylsulfonium salts, and sulfonium borate salts, 2-nitrobenzyl ester compounds, N-iminosulfonate compounds, imide sulfonate compounds, 2, 6-bis (trichloromethyl) -1,3, 5-triazine compounds, and dihydropyridine compounds.
Among them, quinonediazide sulfonyl chloride compounds are preferable because of high sensitivity and good solvent solubility. Many quinone diazide sulfonyl chloride compounds are commercially available, and can also be obtained by subjecting an o-quinone diazide sulfonyl chloride compound to a condensation reaction with a hydroxyl compound, an amino compound or the like in the presence of a desalting acid agent, for example, by reacting a polyhydroxy compound with 1, 2-diazonaphthoquinone-4-sulfonyl chloride or 1, 2-diazonaphthoquinone-5-sulfonyl chloride in the presence of a basic catalyst such as triethylamine. As the quinonediazide sulfonyl chloride compound, 1, 2-benzoquinone-2-diazide-4-sulfonyl chloride, 1, 2-naphthoquinone-2-diazide-5-sulfonyl chloride, 1, 2-naphthoquinone-2-diazide-4-sulfonyl chloride, and the like can be selectively used. As the hydroxyl compound as the esterification precursor of the photosensitizer, p-hydroquinone, bisphenol a, 2-bis (4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, resorcinol, pyrogallol, 2,3,4,2',3' -pentahydroxybenzophenone, 2,3, 4-trihydroxybenzophenone, 2,3, 4' -tetrahydroxybenzophenone, 2', 4' -tetrahydroxybenzophenone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) sulfone and the like can be selectively used, but the present invention is not limited thereto. By using such a quinonediazide compound, a photoacid generator having excellent sensitivity to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which is a general ultraviolet ray, can be obtained. As described above, quinonediazide sulfonyl chloride compounds represented by the following formula (9) are preferred in the present invention.
Figure PCTCN2020091095-APPB-000023
The content of the quinonediazide compound is preferably 2 to 40 parts by mass, and more preferably 8 to 30 parts by mass, per 100 parts by mass of the component (a), in order to obtain an optimum resolution and improve a pattern contrast. In the case where the amount is within the above range, the residue after development of the unexposed portion is easily suppressed, and a practical relief pattern can be obtained. Here, the component (B) may be used alone or in combination of two or more.
3. (C): crosslinker component
The (C) crosslinking agent component of the photosensitive polysulfonamide composition of the present inventionIs a crosslinking agent which undergoes a crosslinking reaction with the polysulfonamide polymer of component (A) in the step of heat-curing the positive photosensitive composition. Therefore, compounds that do not react with the other components of the polysulfonamide compositions are preferred. The crosslinking agent usually contains at least one compound having a-CH group 2 Alkoxy compounds, hydroxyl compounds, epoxy compounds, oxetane compounds OR vinyl ether compounds of OR (R is a hydrogen atom OR a 1-valent organic group). 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 PCTCN2020091095-APPB-000024
The content of the crosslinking agent (C) is preferably 5 to 50 parts by mass, and more preferably 10 to 30 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 crosslinking agent is less than 5 parts by mass, the effect of significantly improving the resistance to corrosion by chemical agents is not obtained; 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): 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.,. Alpha. -dimethylbenzyl) phenyl ] -benzotriazole, 2- (3, 5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -benzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2-octylphenyl) benzotriazole, 5-tert-methylphenyl) benzotriazole, 4-carboxymethylbenzotriazole, 5-H-benzotriazole, 4-tolyltriazole, 4-N-tolyltriazole, 4-1H-triazole, 5-hydroxy-1H-triazole, 5-methylphenyl, 5-1H-triazole, 5-hydroxy-benzotriazole, and the like, 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 PCTCN2020091095-APPB-000025
The content of the corrosion inhibitor (D) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the component (a), in order to obtain an optimum effect of inhibiting metal corrosion.
5. (E): tackifier
In order to improve the adhesion between a cured film formed from the photosensitive resin composition of the present invention and a substrate, an adhesion promoter (E) and a thickener component may be optionally blended in the photosensitive resin composition. (E) 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. From the viewpoint of improving the adhesion force to a substrate such as copper, it is preferable to use an organic silane compound. 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 may be used alone, or 2 or more kinds thereof may be used in combination.
The content of the thickener (E) 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 to the substrate.
6. (F) component (A): solvent(s)
(F) Component (A) to (E) are dissolved in a solvent to form a varnish. (F) 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 positive photosensitive composition and is suitable for a photolithography process. Some common solvents include N-methyl-2-pyrrolidone, γ -butyrolactone, ε -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, 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.
(F) 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), mainly from the viewpoint of controlling the film thickness.
7. Other ingredients of the composition
The resin composition of the present invention may contain, in addition to the above components (a) to (F), other components such as a dissolution accelerator, a dissolution inhibitor, a surfactant, 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. These components and effects are described in detail below.
In the positive type polysulfonamide composition herein, the dissolution promoter can increase the dissolution rate of the exposed portion to thereby improve 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, linear or non-linear phenolic compounds, phenolic substitutes of 2 to 5 for diphenylmethane, phenolic substitutes of 1 to 5 for 3, 3-diphenylpropane, and the like. 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).
The present invention may contain a dissolution inhibitor component that inhibits dissolution of the polysulfonamide. The solvent inhibitor component is not particularly limited as long as it can reduce the dissolution rate of the component (A) in the alkaline aqueous solution. The dissolution inhibitor regulates the development time and film thickness loss by reducing the solubility of the (a) component in the exposure dark space. Compounds commonly used as antisolvents include diphenyliodonium tetrafluoroborate, diphenyliodonium nitrate diphenyliodonium tetrafluoroborate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxyphenyliodonium tetrafluoroborate, 4-methoxyphenyliodonium hexafluorophosphate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, and the like. In the present invention, diphenyliodonium nitrate (12-1), diphenyl-, 9, 10-dimethoxy-2-anthracenium sulfonate (12-2), diphenyliodonium triflate (12-3) represented by the following formula (12) are preferred.
Figure PCTCN2020091095-APPB-000026
The content of the solvent inhibitor component in the composition is preferably 0.01 to 50 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the component (A), from the viewpoint of the overall effect of resolution, development time and film thickness loss.
In order to improve coatability and surface smoothness in spin coating film formation, a surfactant may be added to the composition as a leveling agent, and examples of the film-forming active agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, organosiloxanes, 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, based on 100 parts by mass of the component (a).
The following are preferred examples of the positive photosensitive composition containing polysulfonamide polymers of this invention.
Example 1: the polymer-1 (100 parts by mass) obtained in synthesis example 1, B-1 (10 parts by mass, relative to the polymer-1) as a photoacid, C-3 (20 parts by mass) as a crosslinking agent, D-1 (2 parts by mass) as an anticorrosive agent, and E-1 (3 parts by mass) as a tackifier were dissolved in γ -butyrolactone (160 parts by mass), and H-1 (0.05 parts by mass) as a surfactant was added to obtain a photosensitive positive-working resin composition according to the present invention. Then filtered through a 3 micron PTFE filter to give the varnish. The information on the other components than the polymer component (A) is referred to below:
Figure PCTCN2020091095-APPB-000027
(D-1): 1H-benzotriazole
(D-2) 2- (2H-benzotriazol-2-yl) p-cresol
(D-3) 5-methyl-1H-benzotriazole
(E-1) 3- [ bis (2-hydroxyethyl) amino ] propane-triethoxysilane
(E-2) 3- (2, 3-glycidoxy) propyltrimethoxysilane
(F-1): gamma-butyrolactone
(G-1) Diphenyliodonium nitrate (see the above formula-12)
(G-2) Diphenyl-, 9, 10-dimethoxy-2-anthraiodonium sulfonate (see the above formula-12)
(G-3) Diphenyliodotrifluorosulfonate (see the above formula-12)
(H-1) PF-6320 (fluorosurfactant, omnova Solutions)
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 varnish components described in these examples/comparative examples and their parts by mass (information in parentheses) relative to the polymer (A) (100 parts by mass) are specified in Table-1 below.
TABLE-1
Figure PCTCN2020091095-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 to obtain final positive 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 may be selected.
The varnish is then formed into a polysulfonamide resin film of about 10 μm thickness coated 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, the development is performed by a method such as a dipping method or a spin spray method. In the case of using the positive photosensitive resin composition of the present invention, the developer can remove the exposed 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 a quaternary ammonium salt such as tetramethylammonium hydroxide (TMAH) or tetrabutylammonium hydroxide may also be used. In the above-mentioned various developing solutions, a suitable amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added as necessary to enhance the effect. Of these developing solutions, 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 appropriately diluted to adjust the film dissolution rate of the exposed region and the non-exposed region 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 a high-purity nitrogen gas (. Gtoreq.99.999%) atmosphere.
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. Examples of 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 touch Pad electrode) and the outside (Solder Bump: solder ball). The two-layer wiring structure is realized by copper redistribution layer leads (Cu RDLs) wrapped on polymer layers (polymer layer 1 and polymer layer 2) of insulating material. As shown in fig. 1, copper leads connect the aluminum sheet contact plate electrodes (Al Pad) 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 product film described in 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 component such as a semiconductor device, a multilayer wiring board, and the like 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. The invention adopts the following American Society for Testing and Materials (ASTM) standard method to evaluate the adhesiveness of the material: d3359 Standard method for testing pasting lines with Tape (Standard Test Methods for Measuring Adhesion by Tape Test). The specific operation details are as follows: the resulting cured film (on the copper substrate) without the relief pattern was cut into small 10 × 10 lattice-like cells (1 mm × 1 mm per cell area) in the vertical direction with a saw-tooth-shaped louver 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 a material film to a 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 product 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 copper color under the cured film clearly shifts to deep red/brown, it is evaluated as B that discoloration is 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 metals. Here, the component D (anticorrosive agent) plays a key role in suppressing the discoloration of copper metal, and when the component D is 0.5 parts by mass or 0 parts by mass in the composition, the polysulfonamide cured film cannot effectively suppress 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 Adhesiveness Discoloration inhibition
Example #1 A A
Example #2 A A
Example #3 A A
Example #4 A A
Example #5 A A
Example #6 A A
Example #7 A A
Example #8 A A
Example #9 A A
Example #10 A A
Example #11 A A
Example #12 Film peeling Film peeling
Example #13 A A
Example #14 A A
Example #15 A B
Example #16 A A
Example #17 Film peeling Film peeling
Example #18 A A
Example #19 A A
Example #20 A B
Example #21 A A
Example #22 A A
Example #23 A A
Example #24 A A
Example #25 A A
Comparative example #1 A B
Comparative example #2 A A
Comparative example #3 Can not form a film Fail to form a film
Comparative example #4 Film peeling Film peeling
Comparative example #5 A 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 PCTCN2020091095-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 PCTCN2020091095-APPB-100002
    wherein R is 1 ，R 2 ，R 3 ，R 4 Each represents a hydrogen atom or a monovalent organic group;
    Figure PCTCN2020091095-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 PCTCN2020091095-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 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 PCTCN2020091095-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 positive photosensitive composition comprising 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 2 to 40 parts by mass, more preferably 8 to 30 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 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, relative to 100 parts by mass of the component (a);
    (D) Corrosion inhibitor: the content thereof in the composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the component (a);
    (E) Tackifier: the content thereof in the composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, relative to 100 parts by mass of the component (a); and
    (F) 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 positive photosensitive composition containing a polysulfonamide polymer as claimed in claim 4, wherein the component (B) is at least one photoacid generator selected from one or more of a quinonediazide compound, a sulfonate compound, or a triphenylsulfonium salt compound; 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 component (D) is at least one compound having a triazole ring, an imidazole ring and a thiazole ring skeleton, which contains a carbon atom and a nitrogen atom; and/or
    Wherein the component (E) is at least one of an organosilane compound-containing or aluminum-based adhesion promoter; and/or
    Wherein the components of said composition are dissolved in a solvent (F) 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 cured product having a relief pattern, prepared from the positive photosensitive composition containing a polysulfonamide polymer as claimed in any of claims 4 to 5, by a process comprising:
    (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 exposed region of the coating layer to thereby 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 an embossed pattern according to any one of claims 6 to 8, which is applied to a redistribution layer, an interlayer insulation 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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