TWI802540B - Polysulfonamide redistribution compositions and methods of their use - Google Patents

Abstract

The invention relates to polysulfonamide compositions for use as redistribution layers as used in the manufacture of semiconductors and semiconductor packages. More specifically it relates to photoimageable polysulfonamide composition for redistribution applications. The invention also relates to the use of the compositions in semiconductor manufacture.

Description

Polysulfonamide redistribution compositions and uses thereof

This invention relates to polysulfonamide compositions for redistribution layers used in semiconductor manufacturing and semiconductor packaging. More specifically, the present invention relates to photodevelopable compositions for rewiring applications. The invention also relates to the use of the composition in the manufacture of semiconductors.

An integrated circuit (IC) is a group of circuits fabricated on a semiconductor, especially silicon. ICs can be manufactured very compactly, with over 10 million transistors or other electronic components per square millimeter, and this number is growing. As technology advances, the width and size of the wires used to connect transistors and other components to the placement sites on the microcircuit and the connecting wires need to be made smaller and smaller, currently tens of nanometers.

In some cases, when an IC or microchip is manufactured, electrical connections called leads are attached from a microchip to a package housing in which the chip resides using wire bonds. The package housing is then bonded to a circuit board using a variety of techniques, such as J-package, gull-wing package, and solder bump attachment. Many layers of material, both conductive and non-conductive, are required to connect the transistors of the microchip to the package case, circuit board, and the outside world. In these configurations, a redistribution layer is necessary.

A redistribution layer is an additional layer of wiring on the chip and/or the package. The redistribution layer enables the microchip to be connected to other microchips, the package and/or the circuit board. The redistribution layer can be of various thicknesses and resolutions. multiple layers of degrees. Redistribution layers are also used in die stacking technology.

For example, prior to flip-chip bumping, rerouting of wires on IC bond pads has become a common connection process. Bumping is a process that utilizes solder used as solder paste for reflow to create a solder ball or bump. The redistribution layer allows tin-lead bumping on die originally designed for wire bonding. Wire bonding of ICs provides connections that are limited to one direction around the IC, whereas redistribution layer and bumping processes allow the aforementioned connections to spread over a two-dimensional surface on the IC. While stud bumps and plated bumps can tolerate the small size and tight spaces of wire bond pads (eg, 100 micron square pads, 150 micron pitch), solder paste typically requires more than twice that space. Transforming the perimeter of the wire bond pads into an area array of solder bump pads through rerouting can overcome the above obstacles.

In some applications, rerouting provides an attractive method for creating power and ground contacts. The redistribution pads also transform external connections from chip scale to board scale as an alternative to costly multilayer substrates. Wafer-level chip-scale packaging typically reroutes the ball grid array pads as the final external package connection.

Driving rerouting has become more necessary. Further redistribution of bond pads is often required in wafer scale packaging, wafer level packaging, more recently 3D packaging and system in packaging.

A redistribution pad is composed of leads for electrical connection, and is processed by electroplating, vapor deposition, electroless electroplating or a combination of the above. The RDL also requires a material with low dielectric properties to isolate and insulate the interconnect leads. As chips and the packaging and redistribution layers for them get smaller and smaller, material properties need to be able to continuously isolate and insulate the aforementioned lead interconnects. As the size becomes smaller, easier to manufacture, low-cost, repeatable and controllable processing methods are also required.

In many cases, polyimides are used in redistribution layers, as well as silicones, benzocyclobutenes, and other exotic and expensive materials, each of which has some level of complexity in synthesis and processing.

Therefore, there is a need to improve the materials and processes used to meet the technical requirements of old and new integrated circuits, especially in the redistribution area.

Novel photodevelopable compositions are disclosed and claimed herein for use as low dielectric materials suitable for redistribution layers. Methods of using the novel compositions are also disclosed and claimed herein, including inkjet and dry film applications.

The photodevelopable composition disclosed and claimed in the first embodiment comprises at least one first arylsulfonamide polymer, whose chemical formula (1) is:

wherein ^R to ^R may be the same or different groups, and are hydrogen, branched or unbranched and substituted or unsubstituted alkyl groups of 1 to 16 carbon atoms (with or without one or different atoms substituting multiple carbon atoms in the chain), substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted fused aryl groups or fused heteroaryl groups groups, substituted or unsubstituted cycloalkyl groups (with or without one or more heteroatoms replacing atoms in the ring), halogens, oxygen group elements, nitrogen group elements, sulfur oxides, phosphorus oxides, silicon and silicon oxide; Y is an aryl group or an aryl group chain, X is an oxygen group element, a nitrogen group element, a sulfur oxide, a phosphorus oxide, silicon or a silicon oxide; at least one crosslinking component; at least one photoacid A generating agent and at least one solvent, wherein the composition has a dielectric coefficient of less than 4.0 when processed.

In the second embodiment, the chemical formula (2) of Y in the composition of the above-mentioned embodiment disclosed and claimed is:

Wherein R ⁹ to R ¹⁶ may be the same or different groups, and are hydrogen, branched or unbranched and substituted or unsubstituted alkyl groups of 1 to 16 carbon atoms (with or without one or different atoms substituting multiple carbon atoms in the chain), substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted fused aryl groups or fused heteroaryl groups groups, substituted or unsubstituted cycloalkyl groups (with or without one or more heteroatoms replacing atoms in the ring), halogens, oxygen group elements, nitrogen group elements, sulfur oxides, phosphorus oxides, silicon and silicon oxide; and Y' is a chemical bond, a carbonyl group, an oxygen group element, a nitrogen group element, sulfur oxide, phosphorus oxide, silicon or silicon oxide.

In a third embodiment is disclosed and claimed the composition of the above embodiments, wherein the first arylsulfonamide polymer has a molecular weight between about 20,000 and 200,000, and when the composition is coated and dried Soluble in alkaline solution during the process.

In the fourth embodiment, the composition of the above embodiments is disclosed and claimed, wherein the composition further comprises at least one softener, a solubility modifier, an adhesion promoter or a combination thereof.

In the fifth embodiment, the composition of the above embodiment is disclosed and claimed, wherein the composition further comprises at least one second arylsulfonamide polymer, which has the chemical formula (1), wherein X is an oxygen group element, nitrogen group Elements, sulfur oxides, phosphorus oxides, silicon and silicon oxides; Y is chemical formula (2); wherein R ¹ to R ¹⁶ can be the same or different groups, and are hydrogen, branched or unbranched and Substituted or unsubstituted alkyl groups of 1 to 16 carbon atoms (with or without one or more heteroatoms substituting chain carbon atoms), substituted or unsubstituted aryl groups, substituted or unsubstituted Heteroaryl groups, substituted or unsubstituted fused aryl groups or fused heteroaryl groups, substituted or unsubstituted cycloalkyl groups (with or without one or more substituted ring atoms heteroatom), halogen, oxygen group element, nitrogen group element, sulfur oxide, phosphorus oxide, silicon and silicon oxide; and Y' is a chemical bond, a carbonyl group, an oxygen group element, a nitrogen group element, sulfur oxide substance, phosphorus oxide, silicon or silicon oxide, wherein the at least one second arylsulfonamide polymer has a higher solubility in alkaline developer than the at least one first arylsulfonamide polymer.

In the sixth embodiment, the composition of the above embodiments is disclosed and claimed, wherein at least one photoacid generator comprises an onium salt compound, an argyle imine compound, a halogen-containing compound, an argenyl compound, and a sulfonate compound, a quinonediazide, a diazomethane or a triphenylconium salt.

In a seventh embodiment, the composition of the above embodiments is disclosed and claimed, wherein the at least one crosslinking agent comprises at least one glycidyl ether, one glycidyl ester, one glycidylamine, one methoxymethyl group, one Ethoxymethyl group, a butoxymethyl group, a benzylmethoxy group, a dimethylaminomethyl group, a diethylaminomethyl group, a dibutoxymethyl group , a dimethylolaminomethyl group, a dihydroxyethylaminomethyl group, a dihydroxybutylaminomethyl group, a morpholinomethyl group, an acetyloxymethyl group, a benzyl Oxymethyl group, a formyl group, an acetyl group, a vinyl group or an isopropene group or one or more glycidyl ether groups attached to a phenolic resin, a phenolic, a polyhydroxy Styrene, a polyacrylate or a maleic anhydride ester acid polymer.

In an eighth embodiment the composition of the above embodiments is disclosed and claimed, wherein the at least one solvent comprises esters, ethers, ether esters, ketones, ketoesters, hydrocarbons, aromatic compounds or halogenated solvents.

In a ninth embodiment disclosed and claimed in the composition of the above embodiments, wherein the at least one crosslinking agent comprises an acid-sensitive monomer or polymer, wherein the acid-sensitive group can be at least one tertiary carbonyl, a tertiary Alkyl carbonate or monovinyl ether.

In a tenth embodiment, a process for forming a redistribution layer is disclosed and claimed, comprising a number of steps: providing a substrate, applying the aforementioned photosensitive developing composition to the substrate to a desired wet thickness, using standard techniques (e.g. , spin coating), heating the coated substrate to remove most of the solvent and achieve a desired thickness, image-wise exposing the coating to actinic radiation, removing unexposed areas of the coating, and selectively heating The remaining coating, and optionally, the imagewise exposed coating is heated prior to removing the unexposed areas of the coating. Unexposed areas can be removed with an alkaline developer such as tetramethylammonium hydroxide or a suitable organic solvent developer.

In further embodiments, the composition is applicable for use in inkjet technology or dry film technology.

FIG. 1 shows a scanning electron microscope image produced by the composition and the process of Example 1.

FIG. 2 shows a scanning electron microscope image produced by the composition and the process of Example 2.

FIG. 3 shows a scanning electron microscope image produced by the composition and the process of Example 3.

As used herein, the conjunction "and" is meant to be inclusive, and the conjunction "or" is not meant to be exclusive, unless otherwise stated, for example, the word "or, alternatively" is meant to be exclusive.

As used herein, the term "and/or" refers to any combination of the aforementioned elements, including the use of a single element.

As the terms are used herein, "composition" and "formulation" are used interchangeably and mean the same thing.

As the term is used herein, "solvent" refers to a liquid medium in which one or more various formulation ingredients can be dissolved, colloidally suspended or emulsified.

As the term is used herein, aliphatic may refer to branched or unbranched, saturated or unsaturated, cyclic or polycyclic alkyl, alkenyl or alkyne groups and combinations of these, for example, methyl , ethyl, propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, cyclohexyl, adamantyl and the like. The above-mentioned groups may have substituents attached to their chains and/or their side groups. They may also contain heteroatom substituents in the chain, for example divinyl oxides containing a heteroatom of oxygen in the chain. Heteroatoms include, for example, oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus, silicon, germanium, boron, aluminum and transition elements of the periodic table and their derivatives, such as SO, SO ₂ , S _x , SnH ₂ , N _x and Analogs thereof, wherein x can be 2-6.

As the term is used herein, a heterocycle (alone or in combination with a heterocycle) refers to an optionally substituted aromatic monogroup containing a skeleton of about 4 to 22 ring atoms, wherein one or more The ring atoms are independently selected from oxygen, nitrogen, sulfur, phosphorus, silicon, selenium, tellurium, silicon, germanium, boron, aluminum and transition elements of the periodic table and derivatives thereof, e.g., _Sx , _Nx , SO, SO ₂ and _SiO2 , but not limited to these atoms, with the proviso that the ring does not contain two adjacent O or S atoms. When there are two or more heteroatoms in the ring, in certain embodiments, the two or more heteroatoms are the same, and in certain embodiments, the two or more Some or all of the heteroatoms are different. The term also includes fused heteroaromatic groups and non-fused heteroaromatic groups optionally substituted with at least one heteroatom as described above. In some embodiments, the bond to the heteroaromatic group is through a carbon atom of the heterocyclic ring, and in some embodiments, through a heteroatom of the ring. When available, heteroaromatic rings may be substituted on one or more carbon atoms or on one or more heteroatoms. Fused heteroaromatic rings can contain 2 to 4 fused rings. Heterocycles of the prior disclosure include, for example, monocyclic, pyridyl; fused ring, carbazolyl, benzimidazolyl, quinolinyl, acridinyl; and non-fused bis-heteroaryl, bipyridyl . Other examples include furyl, thienyl, oxazolyl, phenazinyl, benzofuryl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, benzothiophenyl, benzoxa Diazolyl, benzotriazolyl, imidazolyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, purinyl, oxazinyl, pteridinyl, quinolinyl, quinazolinyl , quinoxalinyl, triazolyl, tetrazolyl, thiazolinyl, triazinyl, thiadiazolyl and their analogs and derivatives, for example, their oxides.

As the term is used herein, removal of a substantial portion of the solvent means through heat, at least 92% of the solvent is removed after the composition has been heated.

As used herein, the terms "having", "containing", "including", "comprising" and the like are open-ended terms, which mean that elements or features described now do not exclude additional elements or features. As used herein, "a" and "the" are meant to include both the plural and the singular, unless the context clearly states otherwise.

The previously disclosed photosensitive developing composition comprises at least one first arylsulfonamide polymer, and its chemical formula (1) is:

wherein ^R to ^R may be the same or different groups, and are hydrogen, branched or unbranched and substituted or unsubstituted alkyl groups of 1 to 16 carbon atoms (with or without one or different atoms substituting multiple carbon atoms in the chain), substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted fused aryl groups or fused heteroaryl groups groups, substituted or unsubstituted cycloalkyl groups (with or without one or more heteroatoms replacing atoms in the ring), halogens, oxygen group elements, nitrogen group elements, sulfur oxides, phosphorus oxides, silicon and silicon oxide; Y is an aryl group or an aryl group chain, X is an oxygen group element, a nitrogen group element, a sulfur oxide, a phosphorus oxide, silicon or a silicon oxide; at least one crosslinking component; at least one photoacid A generating agent and at least one solvent, wherein the composition has a dielectric coefficient of less than 4.0 when processed. Y can be chemical formula (2);

Wherein R ⁹ to R ¹⁶ may be the same or different groups, and are hydrogen, branched or unbranched and substituted or unsubstituted alkyl groups of 1 to 16 carbon atoms (with or without one or different atoms substituting multiple carbon atoms in the chain), substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted fused aryl groups or fused heteroaryl groups groups, substituted or unsubstituted cycloalkyl groups (with or without one or more heteroatoms replacing atoms in the ring), halogens, oxygen group elements, nitrogen group elements, sulfur oxides, phosphorus oxides, silicon and silicon oxide; and Y' is a chemical bond, a carbonyl group, an oxygen group element, a nitrogen group element, sulfur oxide, phosphorus oxide, silicon or silicon oxide.

The prior disclosed compositions have a dielectric constant of less than about 4.0 after being processed into a redistribution layer such that the redistribution layer can serve as an insulator for microchip interconnects. The high dielectric constant of the composition facilitates other aspects of microchip processing.

In some aspects of the present disclosure, when the photosensitive development composition is in the coating and drying process and before the photosensitive development composition is exposed to the aqueous developer composition, the photosensitive development composition is exposed to certain alkaline Soluble in solution, for example, in tetramethylammonium hydroxide (TMAH) solution at a concentration of 2.38% wt/wt. For example, depending on the developer and its strength, certain compositions can be formulated to have a pKa value of less than about 12.9 when in the coating and drying process. Certain ingredients can be added to the photodevelopable composition to provide the composition with a desired pKa value, or to increase/decrease the solvency of the composition. In other aspects, organic solvents can be used to develop the photosensitive developing composition.

The first arylsulfonamide polymer may have a suitable molecular weight between 20,000 and 200,000 Daltons. Molecular weight can also be varied to provide desired properties such as solubility in developers, higher or lower dielectric constant, elasticity, and environmental stability.

Useful photoacid generators (PAGs) disclosed in the prior invention include photoacid generators known in the industry, but are not limited to onium salt compounds, for example, caldium salts, phosphonium salts or iodide salts, nonionic compounds, phosphonium Imine compounds, halogen-containing compounds, sulfonate compounds, oxime sulfonic acid, ester sulfonic acid compounds, quinone diazide compounds, diazomethane compounds, dicarboxyimido sulfonate, ylidene aminooxy sulfonate, Sulfonyl azomethane or mixtures of the above substances.

Cross-linking agents used in the present disclosure include (but are not limited to) aminoplasts, such as monomeric or oligomeric melamine, guanamine, urea, methylol, monomeric or oligoglycouril, hydroxyalkylamide, Epoxy and epoxy amine resins, blocked isocyanates and divinyl monomers. Other examples of useful crosslinking compounds are compounds with multiple vinyloxy groups, which can be used as vinyl ether blocked crosslinkers. Other useful crosslinking agents include epoxy materials such as bisphenol A based epoxies, bisphenol F based epoxies, bisphenol S based epoxies, novolac based epoxies, poly(hydroxystyrene) based epoxy compound. Depending on the desired properties of the final film, the crosslinked polymer additives can be used alone or in combination with each other. Crosslinked polymers contain any of a number of identical or different crosslinking substituents, such as epoxy, hydroxyl, thiol, amine, amide, imide, ester, ether, urea, Carboxylic acids and anhydrides and their analogues. Other examples of crosslinking groups include glycidyl ether groups, glycidyl ester groups, glycidylamino groups, methoxymethyl groups, ethoxymethyl groups, phenoxymethyl groups, dimethyl Aminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, dihydroxyethylaminomethyl group, morpholinomethyl group, acetyloxymethyl group, benzyloxymethyl group group, formyl group, acetyl group, vinyl group, isopropene group and vinyl ether group.

Other useful crosslinking agents include monomeric and polymeric hydroxy compounds, as well as monomeric and polymeric phenolic or phenolic resin compounds, as well as polyacrylate and maleic anhydride ester acid polymers. Hydroxyl groups can be protected with acid sensitive protecting groups. When acid treatment is performed, the protecting group is removed from the hydroxyl group. In the prior disclosure, PAGs generate acids when exposed to actinic radiation of appropriate wavelengths. The acid then unblocks the protected hydroxyl groups, which are then free to crosslink in the photodeveloping composition. Acid sensitive groups known in the industry are included and include, but are not limited to, tertiary alkyl esters, tertiary alkyl carbonyls, tertiary alkyl carbonates, e.g., tertiary butoxycarbonate and its analogues.

Solvents useful in the present disclosure include, for example, esters, ethers, ether esters, ketones, ketoesters, hydrocarbons, aromatics, and halogenated solvents, as well as solvents with one or more polar functional groups, such as hydroxyl, Ether, amide, ester, ketone, and carbonic acid, for example, two functional groups that may be the same or different, such as two hydroxyl groups or one hydroxyl group and one ether group. selected from polyols, glycol ethers, diacetone alcohol, 2-pyrrolidone, N-methylpyrrolidone, ethyl lactate, propylene carbonate, 1,3-dimethyl-2-imidazolidinedione and alkyl A group consisting of esters and any combination of the above substances.

For example, the polyol is selected from the group consisting of polyethylene glycol, polypropylene glycol, poly(ethylene-co-propylene glycol), polyvinyl alcohol, trimethylolpropane, ethylene glycol, glycerol, diethylene glycol, triethylene glycol, tripropylene glycol, Tetraethylene glycol, pentaethylene glycol, 1,2-propanediol, 1,3-propanediol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiethylene glycol, hexanediol, bis- 2-Hydroxyethyl ether, 1,4-butanediol, 1,2-butenediol, 1,4-butenediol, 1,3-butenediol, 1,5-pentanediol, 2,4-pentanediol, 2,4-heptanediol, 1,8-octanediol, 1,10-decanediol, 1,12- Dodecanedioxane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-bis(hydroxymethyl)cyclohexane, 1,2-bis(hydroxyethyl)- Cyclohexane, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, pentaerythritol, sorbitol, mannitol and the above The group formed by any combination of polyols, and preferably, the polyhydric alcohol is selected from polyethylene glycol, trimethylolpropane, ethylene glycol, glycerin, diethylene glycol, tripropylene glycol and any combination of the above substances group.

Ethylene glycol ether is selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, propylene glycol n-propyl ether, propylene glycol tert-butyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol n-propyl ether, dipropylene glycol tert-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-propyl ether, tripropylene glycol tert Butyl ether, tripropylene glycol n-butyl ether, ethyl cellosolve, methyl cellosolve, polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, methoxy triethylene glycol, ethoxy triethylene glycol Alcohol, butoxytriethylene glycol, 1-butoxyethoxy-2-propanol and any combination of the above substances, and preferably, the glycol ether is selected from ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and any combination of the above substances . In an embodiment of the present invention, propylene glycol monomethyl ether is a humectant.

Other components of the photodevelopable composition may include, for example, at least one of softener, dissolution rate regulator, leveler, surfactant or adhesion promoter. Softeners include polyols of different molecular weights, polyesters and polyol esters and the like. Adhesion promoters are known in the industry and vary depending on the surface to which the photodevelopable composition is applied. For example, a suitable adhesion promoter for silicon surfaces is epoxysilane. Surfactants and levelers suitable for use in the compositions of the present disclosure are fluorinated surfactants and others known in the art.

In certain embodiments, solubility modifiers may also be included in the photosensitive developing compositions of the present disclosure, such as to aid in developing unexposed areas of the coating when processed. They can range from materials with high pKa values suitable for alkaline developers, such as phenolic resins, such as cresol-cresol Aldehyde resins and carboxylic acid-containing materials such as acrylic acid-containing polymers. The molecular weight of these modifiers can range from about 100 to 100,000 Daltons.

In certain embodiments, dissolution rate inhibitors may be used to prevent the developer from attacking the cured portion of the coating. Examples include maleic acid-containing polymers and copolymers, and maleic acid-containing polymers and copolymers may be modified to include ester groups.

In other embodiments, the solubility modifier can be based on aryl sulfonamide polymers, the aryl sulfonamide polymers have the chemical formula (1), wherein X is an oxygen group element, nitrogen group element, sulfur oxide, phosphorus oxide , silicon or silicon oxide; Y is chemical formula (2); wherein R ¹ to R ⁸ can be the same or different groups, and are hydrogen, branched or unbranched and substituted or unsubstituted 1 to 16 Alkyl groups of carbon atoms (with or without one or more heteroatoms substituting chain carbon atoms), substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or Unsubstituted fused aryl or fused heteroaryl groups, substituted or unsubstituted cycloalkyl groups with or without one or more heteroatoms substituting ring atoms, halogens, oxygen elements , nitrogen group elements, sulfur oxides, phosphorus oxides, silicon and silicon oxides; and Y' is a chemical bond, a carbonyl group, an oxygen group element, a nitrogen group element, sulfur oxides, phosphorus oxides, Silicon or silicon oxide, wherein the solubility of the sulfonamide in the alkaline developer is higher than that of the arylsulfonamide polymer used as the base polymer in the photosensitive developing composition.

Typical ranges (%wt/wt) of ingredients of the photodevelopable composition include arylsulfonamide polymer: 65%-86%, crosslinker: 8.5%-22%, softener, when present: 4.0%- 20.0%, PAG: 0.8%-2.0%, solubility modifier, when present: 0.8%-2.0%, adhesion promoter, when present: 0.8%-1.5%, and surfactant, when present : 0.04%-0.13%.

Disclosed and claimed in other embodiments are methods of using the previously disclosed photosensitive developing composition. A substrate, such as a silicon wafer, is provided, or the wafer may be treated with multiple coatings including adhesion promoters, metal layers, oxide layers, and the like. The wafer may also contain prefabricated structures, such as other dielectric layers, or metal layers, such as copper, aluminum, gold, and the like. and then apply the existing The photodevelopable composition is applied to the surface of the substrate and coated using spin coating, curtain coating, brush coating, dip coating, and the like. The coating can be applied to the surface of the substrate by inkjet technology, in which case it can be applied to the entire surface of the substrate, or only a part of the surface of the substrate as desired. In this technique, structures as small as about 10 nm can be applied to the surface of the substrate. The coating thickness can be between 1-15 microns. The solvent is removed to less than about 92% by heating (eg, 90°C-110°C for 1-3 minutes).

In other embodiments, the previously disclosed photosensitive and developing compositions may first be prepared as a photosensitive and developing dry film. In preparing a dry film, the composition is coated on an optically transparent support having a transmittance of from 50 to 95% so that the desired actinic radiation can be used to expose the photosensitive developing composition , such as polyethylene terephthalate (PET) film, using methods such as roll coating or other known methods to prepare dry film photoresists. Solvent was removed to about 92%. A protective polyethylene film is then used to cover the photosensitive photodevelopable composition. In use, the polyethylene film is removed and the photodevelopable composition is placed sideways on the substrate, usually by heat pressing. The PET film can be left exposed and laminated to the photodevelopable composition, or it can be removed for non-contact printing.

After the substrate is coated, the photodevelopable composition is exposed to actinic radiation to form the desired pattern. The radiation can be I-line (365nm), G-line, H-line, UV, EUV, electron beam, visible light or other known actinic radiation used in photolithography in the art, eg 125 to 800 mJ/cm ² . The coating can be selectively heated to intensify curing the exposed areas. The unexposed areas are then removed with a suitable developer, either aqueous or organic solvent as described above. The developer can be present at room temperature or elevated temperature. The resulting structure can optionally be heated to increase its robustness, eg, 175-250° C. for 1-5 minutes.

Example 1:

10 parts of arylsulfonamide polymer (3) were added to 100 parts of cyclopentanone. 3.2 parts of Powderlink® 1174 from Eastman Chemical, 2.5 parts of CDR 3314 from King Industries, 0.3 Parts of p-n-octyloxyphenyl, phenyl iodonium hexafluoroantimonate (para-n-octyloxyphenyl,phenyl iodonium hexafluoroantimonate, OPPI) and 0.3 parts of poly(styrene-co-maleic anhydride) mixed together . The composition was spin-coated onto a silicon wafer to 9.8 microns.

Soft bake the coated wafer at 90°C for 2 minutes. The wafer was exposed to i-line (365nm) radiation at 800mJ/ ^cm2 . The exposed wafer was baked at 105°C for 3 minutes. Unexposed areas were removed using a 2.38% TMAH solution at room temperature. The resulting structure was then thermally cured at 175°C for 1 hour to obtain the pattern shown in Figure 1. The operating conditions to obtain the pattern shown in Figure 1 were: 6 µm lines from a 9.8 µm film; Dose: 800 mJ/cm ² ; PEB: 3 minutes at 105°C.

Example 2:

10 parts of arylsulfonamide polymer (3) were added to a blend of 50 parts of cyclopentanone and 50 parts of 2-heptanone, 1.5 parts of Powderlink® 1174, 1.0 parts of CDR 3314, 0.3 parts of Irgacure® 121, from BASF's nonionic oxime sulfonic acid was mixed with 0.3 parts of poly(styrene-co-maleic anhydride). The composition was spin-coated onto a silicon wafer to 9.8 microns.

Soft bake the coated wafer at 90°C for 2 minutes. The wafer was exposed to i-line (365nm) radiation at 150mJ/ ^cm2 . The exposed wafer was baked at 105°C for 5 minutes. Unexposed areas were removed using a 2.38% TMAH solution at room temperature. The resulting structure was then thermally cured at 175°C for 1 hour to obtain the pattern shown in Figure 2. The operating conditions to obtain the pattern shown in Figure 2 were: dose: 150 mJ/cm ² ; PEB: 5 minutes at 105°C.

Example 3:

Example 1 was repeated using Irgacure 103 non-ionic PAG in place of ionic OPPI PAG. The wafers were processed and exposed to 240 mJ/cm ² and baked at 105° C. for 3 minutes after exposure. The result is shown in Figure 3. The operating conditions to obtain the pattern shown in Figure 3 were: 10 μm film, 10 μm line; dose: 240 mJ/cm ² ; PEB: 3 minutes at 105°C.

The treated composition in this example shows low temperature cure of less than 250°C with a size ratio better than 1, in some cases 2.5:1. Strong adhesion to copper, which is extremely important in RDLs since copper is the ubiquitous metal used for interconnects today. The technical characteristics of the above-mentioned processing flow have also passed the environmental test carried out in 1000 cycles at -55°C~125°C.

Claims (19)

A photosensitive developing composition, comprising: a. at least one first arylsulfonamide polymer, whose chemical formula (1) is:

wherein ^R to ^R may be the same or different groups, and are hydrogen, branched or unbranched and substituted or unsubstituted alkyl groups of 1 to 16 carbon atoms (with or without one or different atoms substituting multiple carbon atoms in the chain), substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted fused aryl groups or fused heteroaryl groups groups, substituted or unsubstituted cycloalkyl groups (with or without one or more heteroatoms replacing atoms in the ring), halogens, oxygen group elements, nitrogen group elements, sulfur oxides, phosphorus oxides, silicon and silicon oxide; Y is an aryl group or an aryl group chain, X is a chemical bond, a carbonyl group, an oxygen group element, a nitrogen group element, a sulfur oxide, a phosphorus oxide, silicon or a silicon oxide, wherein the chemical formula of Y is ( 2) as:

Wherein R ⁹ to R ¹⁶ may be the same or different groups, and are hydrogen, branched or unbranched and substituted or unsubstituted alkyl groups of 1 to 16 carbon atoms (with or without one or different atoms substituting multiple carbon atoms in the chain), substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted fused aryl groups or fused heteroaryl groups groups, substituted or unsubstituted cycloalkyl groups (with or without one or more heteroatoms replacing atoms in the ring), halogens, oxygen group elements, nitrogen group elements, sulfur oxides, phosphorus oxides, silicon and silicon oxide; and Y' is a chemical bond, a carbonyl group, an oxygen group element, a nitrogen group element, sulfur oxide, phosphorus oxide, silicon or silicon oxide; b. at least one second aryl sulfonamide polymerization The compound has chemical formula (1), wherein X is an oxygen group element, nitrogen group element, sulfur oxide, phosphorus oxide, silicon and silicon oxide; Y is chemical formula (2); wherein R ¹ to R ¹⁶ can be The same or different groups, and are hydrogen, branched or unbranched and substituted or unsubstituted alkyl groups of 1 to 16 carbon atoms (with or without one or more substituted chain carbon atoms heteroatoms), substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted fused aryl groups or fused heteroaryl groups, substituted or unsubstituted Cycloalkyl groups (with or without one or more heteroatoms substituting ring atoms), halogens, oxygen group elements, nitrogen group elements, sulfur oxides, phosphorus oxides, silicon and silicon oxides, wherein at least a second arylsulfonamide polymer having a higher solubility in an alkaline developer than the at least one first arylsulfonamide polymer; c. at least one crosslinking component; d. at least one photoacid generator; and e. at least A solvent; wherein the composition has a dielectric constant of less than 4.0 when processed. The composition of claim 1, wherein the at least one first arylsulfonamide polymer has a pKa value of less than about 12.9. The composition of claim 1, wherein the at least one first arylsulfonamide polymer has a molecular weight between about 20,000 to 200,000. The composition according to claim 1, wherein the composition is soluble in an alkaline solution during coating and drying processes. The composition according to claim 1, further comprising at least one softener, a solubility modifier, an acid-sensitive monomer, oligomer or polymer, or an adhesion promoter. The composition as claimed in claim 1, wherein the at least one photoacid generator comprises an onium salt compound, an imine compound, an oxime sulfonic acid, an ester sulfonic acid compound, a halogen-containing compound, an argyle compound, a sulfonate compound, a quinonediazide, a diazomethane or a triphenylpermedium salt. The composition as claimed in claim 1, wherein the at least one crosslinking component comprises at least one glycidyl ether, one glycidyl ester, one glycidyl amine, one methoxymethyl group, one ethoxymethyl group , a butoxymethyl group, a benzylmethoxy group, a dimethylaminomethyl group, a diethylaminomethyl group, a dibutoxymethyl group, a dimethylol Aminomethyl group, one dihydroxyethylaminomethyl group, one dihydroxybutylaminomethyl group, one morpholinomethyl group, one acetyloxymethyl group, one benzyloxymethyl group, A formyl group, an acetyl group, a vinyl group or an isopropene group or one or more glycidyl ether groups are attached to a phenolic resin. The composition according to claim 1, wherein the at least one solvent comprises esters, ethers, ether esters, ketones, ketoesters, hydrocarbons, aromatic compounds or halogenated solvents. The composition according to claim 1, further comprising at least one phenolic resin, one polyhydroxystyrene, one polyacrylate or one maleic anhydride ester acid polymer cross-linking additive. The composition according to claim 5, wherein the solubility modifier comprises at least one phenolic resin, one polyhydroxystyrene, one polyacrylate or one maleic anhydride ester polymer additive. The composition according to claim 5, wherein the acid sensitive monomer or polymer comprises at least one tertiary carbonyl group, one tertiary alkyl carbonate group or one vinyl ether group. A method for forming a redistribution layer comprising the steps of: a. providing a substrate; b. applying the photosensitive developer composition as described in claim 1 to the substrate to a desired wet thickness; c. heating the coating the substrate to remove most of the solvent to obtain the desired thickness of the coating; d. imagewise exposing the coating to actinic radiation; e. removing unexposed areas of the coating; and f. Optionally heating the remainder of the coating. The method of claim 12, further comprising the step of heating the imagewise exposed coating prior to removing unexposed areas of the coating. The method of claim 12, wherein the unexposed areas of the coating are removed with an alkaline developer. The method as claimed in claim 14, wherein the alkaline developing solution is tetramethylammonium hydroxide. The method of claim 12, wherein the unexposed areas of the coating are removed with an organic solvent developer. The method as claimed in claim 12, wherein the composition is used in inkjet technology. A photosensitive developing dry film structure, which comprises the composition as described in Claim 1. A method for forming a redistribution layer, which comprises the following steps: a. providing a substrate; b. applying the photosensitive and developing dry film structure as described in claim 18 on the substrate in a hot-pressing manner; c. exposing the dried film image-wise to chemical radiation; d. removing the carrier of the dried film; e. removing unexposed areas of the coating; and f. selectively heating the remainder of the coating.

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