CN111548496A - Polysulfonamide polymers, low-temperature crosslinked positive-working photosensitive compositions containing polysulfonamide polymers and use thereof - Google Patents
Polysulfonamide polymers, low-temperature crosslinked positive-working photosensitive compositions containing polysulfonamide polymers and use thereof Download PDFInfo
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- H01L23/485—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of lead-in layers inseparably applied to the semiconductor body consisting of layered constructions comprising conductive layers and insulating layers, e.g. planar contacts
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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, crosslinking agents, and solvents. The composition can prepare a polysulfonamide cured material film under the condition of lower curing temperature (less than or equal to 200 ℃), 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
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 cured product in semiconductor packaging.
Background
Innovations in semiconductor technology have seen a gradual shift in recent years from front-end processing to back-end packaging, as transistor scaling, which has traditionally been relied upon for semiconductor technology innovations, has become increasingly difficult. Each miniaturization of technology nodes (nodes) in recent years comes at the expense of an increase in unit transistor cost. From the standpoint of unit transistor cost, moore's law has no longer been applicable to predict the current trends in the semiconductor industry.
Various advanced post-packaging technologies that have been rapidly developed in the last decade have emerged in response to this new industry trend. The main advanced packaging technologies include flip-chip (flip-chip), fan-in (fan-in), fan-out (fan-out), embedded chip (embedded), and the like. These advanced packaging technologies integrate multiple chip or package connections together by means of direct chip-connection chips, chip-connection packages, package-connection packages, and the like. The optimized system integration not only realizes short-distance rapid transmission between signals, but also can effectively reduce the energy consumption and the heat generation of chips and functional devices. Most importantly, the system integration can reduce the integration of a plurality of chips to a smaller area, so that the system integration provides infinite innovation possibility for the mobile computing mainly based on the smart phone.
The advanced packaging techniques described above place more challenging demands on high performance photosensitive polymers for redistribution layers (RDLs). These photosensitive polymers are required to have excellent lithographic properties, and cured films prepared from the photosensitive polymers also have the advantages of high insulating properties, mechanical properties, adhesion, high-temperature stability, low water absorption, high chemical corrosion resistance and the like. In addition, low-temperature curability is becoming one of the most important indicators for evaluating materials in this field. Materials such as photosensitive Polyimide (PI), Polybenzobisoxazole (PBO), benzocyclobutene (BCB), etc., which have been the mainstream in the past, have not been able to meet the requirements of the current latest technology because they require a high post-curing temperature. The low-temperature curing type photosensitive polyimide, polybenzoxazole and benzocyclobutene become major hot spots of research and development of various companies in the electronic material industry in recent years. In addition, the search for new alternative materials with excellent low temperature curability has also attracted increasing attention.
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. In this context, polysulfonamide polymers which have appeared in recent years have proven to have excellent material properties after curing at low temperatures. The composition containing polysulfonamide also has the advantages of small film thickness loss, excellent lithographic performance and the like. On the basis, the invention provides a method for further improving the low-temperature curing performance of the polysulfonamide material. That is, in the synthesis of polysulfonamides, chain-like aliphatic diamine precursors are partially substituted for the aromatic diamine precursors used in the past, thereby increasing the flexibility of the polymer chain and ultimately achieving the goal of lowering the curing 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 novel polysulfonamide polymer mainly used for positive 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 positive photosensitive compositions containing polysulfonamide polymers, which can provide effective crosslinking ability and excellent lithographic performance under a low-temperature (200 ℃ or lower) heat treatment condition, 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 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),
wherein m and n represent the number of structural units in the polymer and are integers of 1-99. In addition, the relation between m and n satisfies that m/(m + n) is more than or equal to 15% and less than or equal to 85%.
X1 in the general formula (1) is a divalent chain linking group, which may be selected from any group represented by the following general formula (2) or a combination of these structures at any ratio;
h, j and k described in the above general formula (2) may be values of 1 to 40, respectively;
x2 in the general formula (1) is a divalent aromatic linking group which may be any one group represented by the following general formula (3), (4) or (5) or a combination of these structures at any ratio;
wherein R is1,R2,R3,R4Each represents a hydrogen atom or a monovalent organic group;
wherein Q is a direct bond or a divalent organic group selected from O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)x(1≤x≤10)、(CF2)y(1≤y≤10)、C(CH3)2、 C(CF3)2Substituted or unsubstituted-o, -m, -p-phenylene, phenylene ether group (C)6H4-O-C6H4)s(1 ≤s≤10);
Wherein T is a direct bond or a divalent organic group selected from O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)x(1≤x≤10)、(CF2)y(1≤y≤10)、C(CH3)2、 C(CF3)2Substituted or unsubstituted-o, -m, -p-phenylene, phenylene ether group (C)6H4-O-C6H4)s(1. ltoreq. s.ltoreq.10), wherein R5~R12Are identical or different monovalent organic radicals selected from H, CH3Or CF3;
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 (6) or (7):
wherein U in the general formula (6) is a direct bond or a divalent organic group selected from O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)x(1≤x≤10)、(CF2)y(1≤y≤ 10)、C(CH3)2、C(CF3)2Substituted or unsubstituted-o, -m, -p-phenylene.
The aforementioned polysulfonamide polymers 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) polyamide sulfonamide polymers;
(B) photoacid generators: the content thereof in the composition is preferably 5 to 40 parts by mass, more preferably 8 to 30 parts by mass, per 100 parts by mass of the component (A);
(C) a crosslinking agent: the content thereof in the composition is preferably 3 to 50 parts by mass, more preferably 5 to 40 parts by mass, per 100 parts by mass of the component (A); and
(D) solvent: the content thereof in the composition is preferably 50 to 600 parts by mass, more preferably 60 to 500 parts by mass, and still more preferably 80 to 300 parts by mass, per 100 parts by mass of the component (A).
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
The positive photosensitive composition containing a polysulfonamide polymer as described above, wherein the component (B) is at least one photoacid generator selected from one or more of quinone diazide compounds, sulfonic acid ester compounds, iodonium salts or triphenylsulfonium salts; and/or
Wherein the component (C) contains at least one compound having a-CH2Alkoxy OR hydroxy compounds of OR (R is a hydrogen atom OR a 1-valent organic group), epoxy compounds, oxetane compounds OR vinyl ether group compounds, and compounds having a hydroxymethyl group OR an alkoxymethyl group are preferable.
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. The positive photosensitive composition containing polysulfonamide polymers according to the present invention can be used for preparing a cured product 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 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.
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 200 ℃ 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 polysulfonamide polymer, a positive photosensitive composition containing the 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, crosslinking agents, and solvents. The composition can prepare a polysulfonamide cured material film under the condition of lower curing temperature (less than or equal to 200 ℃), 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 the technical scheme, the positive photosensitive composition containing the polysulfonamide polymers, the cured product prepared from the positive photosensitive composition and the application of the cured product in semiconductor packaging have at least the following advantages:
in view of the relatively high curing temperatures required for conventional photosensitive dielectric materials, a novel polysulfonamide composition containing a chain-structured diamine precursor is used in the present invention. As a result, it was found that such films can be prepared with films having a relief microstructure under relatively low temperature (200 ℃ C. 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, 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 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 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 will be made on the polysulfonamide polymers, positive photosensitive compositions containing polysulfonamide polymers, cured products prepared therefrom, and their applications in semiconductor packaging according to the present invention with reference to the accompanying drawings and preferred embodiments.
The present invention will be further specifically described below by way of examples of synthesis of polysulfonamide polymers. The present invention is not limited to these polymer synthesis examples, and those having ordinary knowledge in the art can make various modifications within the technical spirit of the present invention.
One, (A) component: polysulfonamide polymers
The properties of the polysulfonamide polymers prepared in Synthesis examples 1 to 6 are described below.
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 1-99. From the viewpoint of film forming property and dissolution rate control, m and n are preferably integers of 5 to 99. In addition, the relation between m and n satisfies that m/(m + n) is more than or equal to 15% and less than or equal to 85%.
X1 in the general formula (1) is a divalent chain linking group which may be any one of the structures represented by the following general formula (2) or a mixture of these structures at any ratio;
h, j and k described in the above general formula (2) may be values of 1 to 40, respectively;
x2 in the general formula (1) is a divalent aromatic linking group which may be different or the same and has a group represented by the following general formula (3), (4) or (5);
wherein R is1,R2,R3,R4Each represents a hydrogen atom or a monovalent organic group;
wherein Q is a direct bond or a divalent organic group selected from O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)x(1≤x≤10)、(CF2)y(1≤y≤10)、C(CH3)2、 C(CF3)2Substituted or unsubstituted-o, -m, -p-phenylene, phenylene ether group (C)6H4-O-C6H4)s(1 ≤s≤10);
Wherein T is a direct bond or a divalent organic group selected from O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)x(1≤x≤10)、(CF2)y(1≤y≤10)、C(CH3)2、 C(CF3)2Substituted or unsubstituted-o, -m, -p-phenylene, phenylene ether group (C)6H4-O-C6H4)s(1. ltoreq. s.ltoreq.10), wherein R5~R12Are identical or different monovalent organic radicals selected from H, CH3Or CF3;
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 (6) or (7):
wherein U in the general formula (6) is a direct bond or a divalent organic group selected from O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)x(1≤x≤10)、(CF2)y(1≤y≤ 10)、C(CH3)2、C(CF3)2Substituted 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 same molar amount as or slightly excessive amount 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 performing 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 150,000. Here, the molecular weight is measured by a Gel Permeation Chromatography (GPC) method and calculated from a standard polystyrene standard curve.
In order to improve the stability of the composition, the main chain end may be capped with a monoacid chloride compound as a capping agent. As the monoacid chloride compound: the compound may be selected from monocarboxylic acids such as 3-carboxybenzenesulfonic acid and 4-carboxybenzenesulfonic acid, and monocarboxylic acid 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, and active ester compounds obtained by reaction of a monocarboxylic acid chloride compound with N-hydroxybenzotriazole and N-hydroxy-5-norbornene-2, 3-dicarboxylimide. The blocking agent may be one or more of the aforementioned compounds.
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 soaking the mixture in aqueous solution of tetramethyl ammonium hydroxide 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 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 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 solidified 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 comprehensive viewpoint of light transmittance, water absorption, alkali solubility and stress, X2 in the general formula (1) is a divalent aromatic linking group, which is preferably a structural unit having a trifluoromethyl group represented by the following general formula (8).
The polysulfonamide compound represented by general formula (1) preferably has a group represented by general formula (9) below from the viewpoint of stress and alkali solubility.
The following are preferred synthetic examples of polysulfonamide polymers of the present invention.
Synthesis example 1:
jeffamine D-400(50mmol) (Huntsman), 3,4' -diaminodiphenyl ether (50mmol), 2-methylpyridine (300mmol) and anhydrous N-methyl-2-pyrrolidone (NMP) (47.25 g) were charged in a four-necked flask with mechanical stirrer, thermometer and high purity nitrogen atmosphere, stirred to complete dissolution (solution turned clear) and cooled to-10 ℃. The solution was kept at a temperature ranging from-10 to-5 ℃ and a mixture of dissolved 4,4' -bis (sulfonyl chloride) diphenyl ether (100mmol) 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-1 and its structural formula is shown below. If all the precursors are effectively involved in the polycondensation and added to the structure of the end product of the reaction, the molar fractions of the structural units are m/(m + n) ═ 0.5 and n/(m + n) ═ 0.5, respectively. According to the data provided by the manufacturer, h.apprxeq.6 in Polymer-1.
(Polymer-1)
Synthesis example 2:
synthesis of Polymer-2 Synthesis was conducted in accordance with Synthesis example 1 except that the diamine monomer and its addition amount were Jeffamine ED-400(40mmol) (Huntsman) and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (60mmol), respectively. Other conditions/procedures were exactly the same as those in Synthesis example 1. The structure of Polymer-2 is listed below: (Polymer-2). If all the precursors are effectively involved in the polycondensation and added to the structure of the end product of the reaction, the molar fraction m/(m + n) should be 40%. According to the data provided by the manufacturer, h.apprxeq.6 in Polymer-1.
(Polymer-2)
Synthesis example 3
Synthesis of Polymer-3 Synthesis example 1 was followed, except that the diamine monomer and its addition amount were ED-600(40mmol) (Huntsman) and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (60mmol), respectively. Other conditions/procedures were exactly the same as those in Synthesis example 1. The structure of Polymer-3 is listed below: (Polymer-3). If all the precursors are effectively involved in the polycondensation and added to the structure of the end product of the reaction, the molar fraction m/(m + n) should be 40%. According to the data provided by the manufacturer, j ≈ 9 and (h + k) ≈ 3.5 in polymer-1.
(Polymer-3)
Synthesis example 4
Synthesis of Polymer-4 Synthesis example 1 was followed, except that the diamine monomer and its addition amounts were 1, 3-bis (3-aminopropyl) tetramethyldisiloxane (15mmol) and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (85mmol), respectively. Other conditions/procedures were exactly the same as those in Synthesis example 1. The structure of Polymer-4 is listed below: (Polymer-4). If all the precursors are effectively involved in the polycondensation and added to the structure of the end product of the reaction, the molar fraction m/(m + n) should be 15%.
(Polymer-4)
Synthesis example 5
Synthesis of Polymer-5 Synthesis example 1 was followed, except that the diamine monomer and its addition amounts were dodecanediamine (70mmol) and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (30mmol), respectively. Other conditions/procedures were exactly the same as those in Synthesis example 1. The structure of Polymer-5 is listed below: (Polymer-5). If all the precursors are effectively involved in the polycondensation and added to the structure of the end product of the reaction, the molar fraction m/(m + n) should be 70%.
(Polymer-5)
Synthesis example 6
Synthesis of Polymer-6 Synthesis of example 1 was repeated, except that the diamine monomer and its added amount were ED-600(60mmol) (Huntsman) and 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3, 3-hexafluoropropane (40mmol), respectively. Other conditions/procedures were exactly the same as those in Synthesis example 1. The structure of Polymer-6 is listed below: (Polymer-6). If all the precursors are effectively involved in the polycondensation and added to the structure of the end product of the reaction, the molar fraction m/(m + n) should be 60%. According to the data provided by the manufacturer, j ≈ 9 and (h + k) ≈ 3.5 in polymer-1.
(Polymer-6)
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 described 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, and (D) 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.
II, and (B) component: 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 the photoacid commonly used in the positive photosensitive composition containing a polysulfonamide polymer include quinone diazide sulfonyl chlorides, 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 condensation reaction of an o-quinone diazide sulfonyl chloride 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 sensitizer, 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, 4' -tetrahydroxybenzophenone, 2 ', 4,4' -tetrahydroxybenzophenone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) sulfone and the like can be selectively used, but is not limited thereto. By using such a quinonediazide compound, a photoacid generator having excellent sensitivity to i-line (wavelength 365nm), h-line (wavelength 405nm), and g-line (wavelength 436nm) 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 (10) are preferable in the present invention.
The content of the quinonediazide compound is preferably 5 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.
Thirdly, component (C): crosslinker component
The crosslinking agent component (C) in the photosensitive polysulfonamide composition of the present invention is a crosslinking agent which undergoes a crosslinking reaction with the polysulfonamide polymer component (a) in the step of heat-curing the positive photosensitive composition. Thus, compounds that do not react with other components of the polysulfonamide compositions are preferred. The crosslinking agent usually contains at least one compound having a-CH group2Alkoxy OR hydroxy compounds of OR (R is a hydrogen atom OR a 1-valent organic group), epoxy compounds, oxetane compounds OR vinyl ether compounds. From the viewpoint of high mechanical properties of the cured film and high reactivity at the time of curing at low temperature, a compound having a hydroxymethyl group or an alkoxymethyl group represented by the following formula (11) is preferable.
The content of the crosslinking agent (C) is preferably 3 to 50 parts by mass, and more preferably 5 to 40 parts by mass, per 100 parts by mass of the component (A), in order to obtain an optimum chemical agent corrosion resistance effect. If the crosslinking agent is less than 3 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.
Fourthly, component D: solvent(s)
(D) Component (C) as a solvent, and the varnish is formed by dissolving the above components (a) to (C). The (D) component may employ a compound comprising at least one 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, -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.
(D) The content of the component (A) is not particularly limited, but is preferably 50 to 600 parts by mass, more preferably 60 to 500 parts by mass, and still more preferably 80 to 300 parts by mass, based on 100 parts by mass of the component (A), mainly from the viewpoint of controlling the film thickness.
Fifthly, other components 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 dissolution accelerator, a solvent retarder, 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.
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 (12) 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, p-tolyltriazole, p, 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 '-hydroxy-5' -tert-octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, p-tolyltriazole, p-, 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.
The content of the corrosion inhibitor 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.
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 tackifier component may be optionally 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, N-tert-butyl-ethyl-methyl-3-aminopropyltrimethoxysilane, N-butyl-ethyl-N-butyl-ethyl-butyl-N-butyl-ethyl, 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 component in the composition is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the component (a), from the viewpoint of improving the adhesion to the substrate.
Dissolution accelerating agent-in the positive type polysulfonamide compositions herein, the dissolution accelerating agent 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, phenol-substituted products of 2 to 5 of diphenylmethane, and phenol-substituted products of 1 to 5 of 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).
Dissolution inhibitors-the present invention may contain a dissolution inhibitor component that inhibits dissolution of the polysulfonamide polymers. 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 tetrafluoroborate, bis, Bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium p-toluenesulfonate, and the like. In the present invention, diphenyliodonium nitrate (13-1), diphenyl-, 9, 10-dimethoxy-2-anthraceneiodonium sulfonate (13-2), diphenyliodonium triflate (13-3) represented by the following formula (13) are preferred.
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.
Surfactants-in order to improve coatability and surface smoothness during spin-on film formation, surfactants may be added to the composition as leveling agents, and examples of film-forming agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, organosilicones, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. Some examples are available directly from the market, including MegafacF171, F173 (manufactured by Dainippon ink chemical industries, Ltd.); 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 examples of the positive photosensitive composition of the present invention containing a polysulfonamide polymer.
Example 1: a positive photosensitive resin composition according to the present invention was obtained by dissolving polymer-1 (100 parts by mass) obtained in Synthesis example 1, B-1(10 parts by mass, based on polymer-1) as a photoacid, C-1(25 parts by mass) as a crosslinking agent, E-1(2 parts by mass) as an anticorrosive agent, F-1(5 parts by mass) as a thickener, and G-1(2 parts by mass) as a solvent retarder in D-1(γ -butyrolactone, 160 parts by mass), and adding H-1(0.05 part by mass) as a surfactant. 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:
(D-1): gamma-butyrolactone
(E-1): 1H-benzotriazole
(E-2) 5-Aminotetrazole
(E-3) 5-methyl-1H-benzotriazole
(F-1) 3- [ bis (2-hydroxyethyl) amino ] propane-triethoxysilane
(F-2) 3- (2, 3-glycidoxy) propyltrimethoxysilane
(G-1) Diphenyliodonium nitrate (see the aforementioned formula-13)
(G-2) Diphenyl-, 9, 10-dimethoxy-2-anthraiodonium sulfonate (see the aforementioned formula-13)
(H-1) PF-6320 (fluorosurfactant, Omnova Solutions)
Examples 2 to 10 and comparative examples 1 to 5 were prepared in exactly the same manner as in example 1 except that the respective components or contents used therein were 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 detailed in the following Table-1.
TABLE-1
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 can be chosen.
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 claim 1 to 5 to a substrate and heating the composition on a hot plate 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 90-150 ℃, and more preferably 90-130 ℃.
(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 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 quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH) and 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. 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 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 as the heating method, and the heating temperature is preferably 200 ℃ or less. 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 this embodiment mode, by designing the two-layer wiring structure, a signal can be input/output between the chip (Al Pad: aluminum contact plate electrode) and the outside (SolderBump: 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 in fig. 1, copper leads connect aluminum pads (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.
Sixth, evaluation of adhesiveness
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 Measuring adhesive attachment by Tape Test. The specific operation details are as follows: the coating film obtained by the above method is heated on a hot plate at 120 ℃ for 3 minutes to obtain a film of about 10 μm; then curing the copper substrate at 200 ℃ to obtain a cured film without the relief pattern on the copper substrate; the cured film was cut into small 10 × 10 lattices (1 mm × 1 mm per lattice area) in the vertical direction with a saw-tooth-shaped hundred-lattice blade. An adhesive tape (manufactured by 3M) was attached to these small pieces of the cured film according to the method described in ASTM D3359, and the adhesive tape was 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 were excellent in adhesion to copper substrates as a whole.
Seventh, 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.
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 | A |
Example #6 | A | A |
Example #7 | A | A |
Example #8 | A | A |
Example #9 | A | A |
Example #10 | A | A |
Comparative example #1 | Can not form a film | Can not form a film |
Comparative example #2 | A | B |
Comparative example #3 | A | B |
Comparative example #4 | Film peeling | Film peeling |
Comparative example #5 | Film dissolution | Film dissolution |
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),
wherein:
m and n represent the number of structural units in the polymer, and are integers of 1-99, and the relationship between m and n satisfies that m/(m + n) is more than or equal to 15 percent and less than or equal to 85 percent; x1 in the general formula (1) is a divalent chain linking group; y in the general formula (1) is a divalent aromatic group.
2. The polysulfonamide polymer according to claim 1, wherein the divalent chain-like linking group represented by X1 in the general formula (1) is selected from any one group represented by the following general formula (2) or a combination of these groups in any ratio;
h, j and k in the above general formula (2) may each be any of values of 1 to 40;
x2 in the general formula (1) is a divalent aromatic linking group selected from any one of the following general formulae (3), (4) or (5) or a combination of these structures in any proportion;
wherein R is1,R2,R3,R4Each represents a hydrogen atom or a monovalent organic group;
wherein Q is a direct bond or a divalent organic group selected from O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)x(1≤x≤10)、(CF2)y(1≤y≤10)、C(CH3)2、C(CF3)2Substituted or unsubstituted-o, -m, -p-phenylene, phenylene ether group (C)6H4-O-C6H4)s(1≤s≤10);
Wherein T is a direct bond or a divalent organic group selected from O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)x(1≤x≤10)、(CF2)y(1≤y≤10)、C(CH3)2、C(CF3)2Substituted or unsubstituted-o, -m, -p-phenylene, phenylene ether group (C)6H4-O-C6H4)s(1. ltoreq. s.ltoreq.10), wherein R5~R12Are identical or different monovalent organic radicals selected from H, CH3Or CF3;
The divalent aromatic group represented by Y in the polysulfonamide polymer of the general formula (1) is selected from structural units represented by the following formula (6) or (7):
wherein U in the general formula (6) is a direct bond or a divalent organic group selected from O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)x(1≤x≤10)、(CF2)y(1≤y≤10)、C(CH3)2、C(CF3)2Substituted or unsubstituted-o, -m, -p-phenylene.
3. The polysulfonamide containing polymer of claim 1 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) polyamide sulfonamide polymers;
(B) photoacid generators: the content thereof in the composition is preferably 5 to 40 parts by mass, more preferably 8 to 30 parts by mass, per 100 parts by mass of the component (A);
(C) a crosslinking agent: the content thereof in the composition is preferably 3 to 50 parts by mass, more preferably 5 to 40 parts by mass, per 100 parts by mass of the component (A); and
(D) solvent: the content thereof in the composition is preferably 50 to 600 parts by mass, more preferably 60 to 500 parts by mass, and still more preferably 80 to 300 parts by mass, per 100 parts by mass of the component (A).
5. The positive photosensitive composition according to claim 4, wherein the component (B) is at least one photoacid generator selected from one or more of, but not limited to, quinone diazide compounds, sulfonate ester compounds, iodonium salts, or triphenylsulfonium salts; and/or
Wherein the component (C) contains at least one compound having a-CH2An alkoxy OR hydroxy compound of OR (R is a hydrogen atom OR a 1-valent organic group), an epoxy compound, an oxetane compound OR a vinyl ether-based compound, preferably a compound having 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-ester hydrocarbons, aromatics, and/or halogenated hydrocarbons.
6. A cured product having a relief pattern prepared from the positive photosensitive composition containing a polysulfonamide polymer according to 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 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 200 ℃ 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, which is applied to a redistribution layer, an interlayer insulating buffer film, a cap coat 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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Cited By (2)
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CN113105631A (en) * | 2021-03-31 | 2021-07-13 | 华南理工大学 | Sulfonamide polymer and preparation method thereof |
CN115433358A (en) * | 2021-07-16 | 2022-12-06 | 山东圣泉新材料股份有限公司 | Polyamide-b-amic acid polymers, positive photosensitive compositions and their use |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113105631A (en) * | 2021-03-31 | 2021-07-13 | 华南理工大学 | Sulfonamide polymer and preparation method thereof |
CN115433358A (en) * | 2021-07-16 | 2022-12-06 | 山东圣泉新材料股份有限公司 | Polyamide-b-amic acid polymers, positive photosensitive compositions and their use |
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