Method for producing resin composition, resin composition, patterning composition, patterning method, and use thereof

Abstract

The application relates to a resin composition preparation method, a resin composition, a patterning composition, a patterning method and application thereof. The method comprises the following steps: mixing an acid solution and a sedimentation solution to obtain an acid mixture; and making a resin-containing liquid composition in the acid mixture to purify the resin-containing liquid composition and obtain a purified resin composition. Compared with the resin-containing liquid composition, the oligomer removal rate of the purified resin composition is 5%-10%, and the weight average molecular weight is increased by 5.2%-9.2%. The pH value of the acid mixture is 3-6, and the mass ratio of the resin-containing liquid composition to the acid mixture is 1:6-1:10. The acid in the acid solution is an organic acid. The sedimentation solution comprises one or more of an alcohol aqueous solution, an alkane solution or an ether solution. Through the method, the emulsification effect can be effectively broken without changing the original sedimentation process, so that solid-liquid separation is effectively realized, and the filtration rate is significantly improved.

Description

Technical Field

[0001] This application relates to the field of patterning, and more specifically, to methods for preparing resin compositions, resin compositions, patterning compositions, patterning methods, and their applications. Background Technology

[0002] With the optimization of integration and performance in electronic devices, patterning technologies used to form these devices continue to evolve towards higher resolutions and smaller feature sizes. However, as key materials for pattern transfer, the performance of patterning materials directly determines the resolution of the patterning process and the precision of electronic device manufacturing. To meet the requirements of immersion patterning materials in terms of optical performance, chemical stability, and water resistance, resin materials such as fluoropolymers are typically introduced into the patterning materials. Fluoropolymers, by regulating the surface properties, chemical stability, thermal stability, optical properties, and moisture resistance of patterning materials, help improve pattern resolution, edge accuracy, and process repeatability, thus making them an indispensable functional component in advanced patterning materials. Purification of resin materials is a crucial path to ensure that the final product meets the expected performance indicators and achieves high-quality output. Using sedimentation technology to remove oligomers and small molecules from the resin can significantly improve product purity and meet the application requirements of patterning technology. In the existing industrial production process, the unique physicochemical properties of fluoropolymers (such as small size, easy adhesion, and difficulty in filtration) may cause problems such as "sticking, leakage, and clogging" in sedimentation filtration, which seriously restricts the continuous and high-yield production of products. Summary of the Invention

[0003] To address the problems in the prior art, this application provides a method for preparing a resin composition, a resin composition, a patterned composition, a patterning method, and their applications. The purification method of this application prevents resin composition adhesion without altering the original sedimentation process, thereby achieving effective solid-liquid separation, significantly improving the filtration rate, and ultimately reducing the production cycle and overall cost.

[0004] In a first aspect, this application provides a method for preparing a resin composition, the method comprising: mixing an acid solution with a precipitation solution to obtain an acidic mixture; and precipitating a resin-containing liquid composition in the acidic mixture to purify the resin-containing liquid composition to obtain a purified resin composition. Compared to the resin-containing liquid composition, the purified resin composition has an oligomer cleavage rate of 5%-10% and a weight-average molecular weight increase of 5.2%-9.2%. The pH value of the acidic mixture is 3-6, and the mass ratio of the resin-containing liquid composition to the acidic mixture is 1:6-1:10. The acid in the acid solution is an organic acid selected from one or more of the following: formic acid, acetic acid, oxalic acid, malonic acid, citric acid, tartaric acid, malic acid, lactic acid, gluconic acid, p-toluenesulfonic acid, trifluoroacetic acid, lactic acid, or benzoic acid. The precipitation solution comprises one or more of an aqueous alcohol solution, an alkane solution, or an ether solution.

[0005] The inventors of this application discovered that when the pH of the acidic mixture is <3, the acidity is too strong, which may cause the monomers on the polymer chain to deprotect, thereby leading to the denaturation of the resin composition; when the pH of the acidic mixture is >6, emulsification occurs, causing the resin composition to stick together and unable to separate. However, when the pH of the acidic mixture is in the range of 3-6, and the mass ratio of the resin-containing liquid composition to the acidic mixture is 1:6-1:10, the resin composition exhibits a normal physical state without resin adhesion during sedimentation, thereby improving the sedimentation filtration effect, shortening the process time, and reducing the overall cost of the purification process.

[0006] Furthermore, when the organic acid used in the method is selected from one or more of the aforementioned acids, it is environmentally friendly because the organic acid is biodegradable. Moreover, using the aforementioned organic acids has advantages such as no ion introduction and easy removal.

[0007] In some embodiments, the settling solution is selected from aqueous alcohol solutions.

[0008] The precipitation solution of the method described in this disclosure, an alcohol-water solution, can further improve the efficiency of removing oligomers from resin-containing liquid compositions.

[0009] In some embodiments, the monomer residue of the purified resin composition is 0.01 wt% to 2.00 wt% based on the total mass of the purified resin composition.

[0010] In some embodiments, the concentration of the acid solution is 2-600 ppm.

[0011] A concentration of 2-600 ppm is considered an extremely low addition level, which is more conducive to the removal of additives.

[0012] In some embodiments, the resin-containing liquid composition comprises a resin polymer, the solid content of which, based on the total mass of the resin-containing liquid composition, is one or more of the following: 30 wt%-35 wt%, 35 wt%-45 wt%, or 45 wt%-50 wt%.

[0013] By controlling the solid content of the resin polymer within the above range, homogeneous polymerization can be achieved in the polymerization system, resulting in a uniform reaction rate, which can avoid explosive polymerization and effectively control the molecular weight distribution of the polymer.

[0014] In some embodiments, the method further includes vacuum filtration, wherein the vacuum filtration is completed in less than 1 minute.

[0015] In this case, the filtration process is completed in a short time, which enables higher production efficiency and facilitates market promotion.

[0016] In some embodiments, the mass ratio of the resin-containing liquid composition to the sedimentation solution is 1:7.

[0017] By setting the above mass ratio of the resin-containing liquid composition to the sedimentation solution, the dispersibility of the resin powder in the sedimentation solution can be further improved.

[0018] In some embodiments, the concentration of the acid solution is one or more of the following: 2-100 ppm, 100-500 ppm, or 500-600 ppm.

[0019] In some embodiments, the sedimentation includes adding the resin-containing liquid composition dropwise to the acidic mixture at one or more of the following temperatures for sedimentation: 15-20°C, 20-25°C, 25-30°C, 30-35°C, or 35-40°C.

[0020] In some embodiments, the duration of the settling is one or more of the following: 20-30 min, 30-40 min, 40-50 min, 50-60 min, 60-70 min, or 70-80 min.

[0021] By controlling the temperature and duration of sedimentation within the aforementioned ranges, the amount of oligomer removed can be effectively controlled, while simultaneously resolving the clogging problem caused by sedimentation adhesion. For example, the good solvent encapsulated in the resin particles can be efficiently released into the sedimentation solvent, causing the particles to harden and thus preventing clogging caused by sedimentation adhesion.

[0022] In some embodiments, the settling solution is selected from at least one of an aqueous methanol solution, an aqueous ethanol solution, an aqueous isopropanol solution, or an aqueous n-butanol solution.

[0023] In some embodiments, the solid content of the resin polymer, based on the total mass of the resin-containing liquid composition and the acidic mixture, is one or more of the following: 3.0 wt%-3.5 wt%, 3.5 wt%-4.5 wt%, or 4.5 wt%-5.0 wt%.

[0024] By maintaining the solids content of the resin polymer within the aforementioned range, unreacted monomers and polymerization solvents can be effectively removed, while resin oligomers can be thoroughly excised, thereby effectively reducing impurity residues. Furthermore, this range can further improve the heat and mass transfer properties of the resin polymer, which is beneficial for reducing system viscosity, thus further preventing explosive polymerization. Additionally, resin polymers with solids content within this range exhibit better solubility.

[0025] Secondly, this application provides a resin composition in which the filtration time for preparing the resin composition is less than 1 minute; the resin composition includes resin and impurities, wherein the impurities are at least one selected from formic acid, acetic acid, oxalic acid, malonic acid, citric acid, tartaric acid, malic acid, lactic acid, gluconic acid, p-toluenesulfonic acid, trifluoroacetic acid, lactic acid, or benzoic acid; and the content of the impurities is greater than 0 and less than 100 ppb.

[0026] Thirdly, this application provides a patterned composition comprising the above-described resin composition and one or more of the following: a photosensitizer, a photoacid generator, or a solvent.

[0027] Fourthly, this application provides a patterning method, the patterning method comprising: forming a patterned film layer using the patterning composition described above; and performing one or more of the following: cleaning, dehydration baking, thin film deposition, exposure, development, or ion implantation.

[0028] Fifthly, this application provides a semiconductor device comprising a functional layer and an optional substrate, wherein the functional layer is fabricated based on the patterned composition described above; the functional layer comprises one or more of a semiconductor layer, a conductive layer, or a dielectric layer.

[0029] In a sixth aspect, this application provides an electronic device comprising: a circuit board; and the aforementioned semiconductor device, wherein the semiconductor device is electrically connected to the circuit board.

[0030] In a seventh aspect, this application provides an electronic device, the electronic device comprising: the above-described electronic device; and at least one of a power supply unit, an interconnection structure, a structural packaging component, and an input / output component.

[0031] In some embodiments, the electronic device is selected from: consumer electronic devices, home electronic appliances, vehicle electronic devices, communication and network equipment, industrial control equipment, medical electronic devices, security and Internet of Things equipment, office and financial equipment, agricultural electronic devices, educational and scientific research electronic devices, new energy and energy storage system equipment, robotics and automated execution equipment, rail transit and intelligent transportation system equipment, and environmental protection and environmental monitoring equipment.

[0032] Compared with the prior art, this application has one or more of the following beneficial effects: The method of this application enables the resin composition to exhibit a normal physical state without resin composition adhesion during the sedimentation process (e.g., the filtration time is less than 1 minute), thereby solving the problem of resin composition clogging during filtration.

[0033] The method described in this application can significantly shorten the production cycle, reduce costs, and improve the overall stability and economy of the process. Attached Figure Description

[0034] Figure 1 This is a diagram of the system after settling in Embodiment 2 of this application.

[0035] Figure 2 This is a diagram of the system after settling in Comparative Example 1 of this application.

[0036] Figure 3 This is a diagram of the system after settling in Comparative Example 2 of this application. Detailed Implementation

[0037] The terms “comprising” or “including” as used herein should be interpreted as having a non-exhaustive meaning and allowing for the addition or reference to further elements, such as adding features or method steps or members or components to anything that includes the listed elements. “Comprising” may be replaced by “including” if the practice of a given language variant requires it, or may be limited to “consistently consisting of” if other elements besides those listed are not essential to the practice of this disclosure, or may be limited to “consisting of” in the absence of any other elements.

[0038] As used herein, the term "patterning" refers to photolithography, a crucial step in electronic device manufacturing. This step involves etching a patterned structure onto a material to be patterned (i.e., a patterning composition) through exposure and development processes. The pattern on the photomask is then transferred to a substrate or substrate using an etching process. This substrate or substrate can include not only silicon wafers but also other metal layers, dielectric layers, and the aforementioned substrates with surface modifications or added supporting layers.

[0039] As used herein, the term "patterned composition" refers to an etching-resistant material whose solubility in a developer changes after being irradiated or exposed to light such as ultraviolet light, deep ultraviolet light, X-rays, electron beams, or ion beams.

[0040] As used herein, the term "developer" refers to a pure or mixed solvent that dissolves soluble areas of a patterned composition after exposure has caused a change in solubility.

[0041] As used in this paper, the term "mask" refers to a mask that serves as an optical element in the optical path during the patterning process. The mask carries the design pattern, and light selectively transmits the design pattern onto the patterned material film through its transmission or reflection.

[0042] As used herein, the term “oligomer” refers to polymers with a weight-average molecular weight (Mw) of less than 1000.

[0043] The term "oligomer resection amount," also known as "oligomer resection rate," used in this article is a relative value obtained through normalized overlay analysis of the spectra obtained by gel permeation chromatography (GPC) before and after purification. For example, the oligomer resection rate is equal to the percentage reduction in the oligomer peak area in the purified sample spectrum compared to the oligomer peak area before purification.

[0044] As used in this article, “filtration complete” means that no more liquid flows out of the filtration device (such as a 5 L settling tank and filtration flask), and the surface of the wet solids (such as filter cake) in the settling tank is cracked or semi-dry (without a clear liquid level).

[0045] As used herein, the term "pre-purification resin composition" refers to the raw polymer solution that has not undergone impurity removal, activation, or specific treatment steps, and may contain synthetic oligomers, unreacted monomers, catalysts, initiators, solvents, etc. The term "post-purification resin composition" as used herein refers to a resin composition that has been treated by steps such as washing, soaking, filtration, vacuum filtration, and drying to remove the aforementioned soluble impurities or specific ions, typically reaching a usable clean state or meeting specific process requirements (e.g., a weight-average molecular weight greater than 6500 Da and a polydispersity index (PDI) less than 1.9, where PDI is the ratio of weight-average molecular weight to number-average molecular weight).

[0046] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0047] In some embodiments of this application, a method for preparing a resin composition is provided, the method comprising: mixing an acid solution with a precipitation solution to obtain an acidic mixture; and precipitating a resin-containing liquid composition in the acidic mixture to purify the resin-containing liquid composition to obtain a purified resin composition. Compared to the resin-containing liquid composition, the purified resin composition has an oligomer cleavage rate of 5%-10% and a weight-average molecular weight increase of 5.2%-9.2%. The pH value of the acidic mixture is 3-6, and the mass ratio of the resin-containing liquid composition to the acidic mixture is 1:6-1:10. The acid in the acid solution is an organic acid selected from one or more of the following: formic acid, acetic acid, oxalic acid, malonic acid, citric acid, tartaric acid, malic acid, lactic acid, gluconic acid, p-toluenesulfonic acid, trifluoroacetic acid, lactic acid, or benzoic acid. The precipitation solution comprises one or more of an aqueous alcohol solution, an alkane solution, or an ether solution.

[0048] This purification method, without altering the original sedimentation process, prevents resin composition adhesion, thereby achieving effective solid-liquid separation, significantly improving the filtration rate, and offering advantages such as short production cycle and low overall cost. Furthermore, by adding a small amount of acid solution, batch stability and high yield production of hundreds of kilograms of resin material can be achieved.

[0049] For example, the resin-containing liquid composition is a resin-containing solution, a resin-containing emulsion, a resin-containing suspension, or a combination thereof.

[0050] For example, the oligomer cleavage rate of the purified resin composition can be 5%, 6%, 7%, 8%, 9%, 10%, or any value between the two.

[0051] For example, the weight-average molecular weight after purification can increase by 5.2%, 6%, 7%, 8%, 9%, 9.2%, or any value between the two above compared to before purification.

[0052] For example, the pH value of the acidic mixture can be 3.00, 3.50, 3.62, 4.00, 4.07, 4.35, 4.36, 4.42, 4.43, 4.50, 4.56, 4.71, 4.82, 4.96, 5.00, 5.50, 6.00, or any value between the two.

[0053] For example, the mass ratio of the resin-containing liquid composition to the acidic mixture can be 1:6, 1:7, 1:8, 1:9, 1:10, or any value between the two.

[0054] In some embodiments, the acid solution may be an aqueous solution of an organic acid.

[0055] In some embodiments, the organic acid in the aqueous solution may be selected from one or more of the following: trifluoroacetic acid, oxalic acid, formic acid, acetic acid, lactic acid, benzoic acid, or citric acid.

[0056] As an example, the alcohol-water solution (i.e., a mixed solution of alcohol and water) may involve a monohydric alcohol, a polyhydric alcohol, a cyclic alcohol, or an alcohol containing heteroatoms. The alkane solution may involve straight-chain alkanes, branched alkanes, cycloalkanes, or mixed alkanes (e.g., petroleum ethers). The ether solution may involve aliphatic ethers, cyclic ethers, aromatic ethers, haloethers, amine ethers, silicone ethers, or polyethers.

[0057] In some embodiments, the settling solution may be selected from aqueous alcohol solutions.

[0058] In some embodiments, the monomer residue of the purified resin composition is 0.01 wt% to 2.00 wt% based on the total mass of the purified resin composition.

[0059] For example, the residual monomer content of the purified resin composition may be 0.01 wt%, 0.02 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.08 wt%, 1.00 wt%, 1.50 wt%, or 2.00 wt%, or any value between the two.

[0060] In some embodiments, the concentration of the acid solution can be 2-600 ppm.

[0061] It is understood that, in this document, the solution formed after the acid solution and the sedimentation solution are mixed is called an "acidic mixture", and the "concentration of the acid solution" refers to the concentration of the acid solution before it is mixed with the sedimentation solution.

[0062] For example, the concentration of the acid solution is 2 ppm, 20 ppm, 40 ppm, 60 ppm, 80 ppm, 100 ppm, 150 ppm, 180 ppm, 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, 500 ppm, 550 ppm, 600 ppm, or any value between the two.

[0063] In some embodiments, the resin-containing liquid composition comprises a resin polymer, the solid content of which, based on the total mass of the resin-containing liquid composition, is one or more of the following: 30 wt%-35 wt%, 35 wt%-45 wt%, or 45 wt%-50 wt%.

[0064] For example, the solid content of the resin polymer is 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt%, or any value between the two.

[0065] For example, the resin polymer may be an acrylic resin polymer, a fluoropolymer, or a poly(p-hydroxystyrene) resin polymer.

[0066] In some embodiments, the method further includes vacuum filtration, wherein the vacuum filtration is completed in less than 1 minute.

[0067] For example, the filtration completion time can be 10 s, 15 s, 20 s, 30 s, 40 s, 50 s, 55 s, or any value between the two mentioned above.

[0068] In some embodiments, the concentration of the acid solution may be one or more of the following: 2-100 ppm, 100-500 ppm, or 500-600 ppm.

[0069] For example, the concentration of the acid solution may be 2-600 ppm or 100-500 ppm.

[0070] In some embodiments, sedimentation includes adding a resin-containing liquid composition to an acidic mixture for sedimentation.

[0071] In some embodiments, sedimentation includes adding a resin-containing liquid composition dropwise to an acidic mixture for sedimentation.

[0072] In some embodiments, the mass ratio of the resin-containing liquid composition to the sedimentation solution is 1:7.

[0073] By setting the above mass ratio of the resin-containing liquid composition to the sedimentation solution, the dispersibility of the resin powder in the sedimentation solution can be further improved.

[0074] In some embodiments, the sedimentation includes dropping a resin-containing liquid composition into an acidic mixture at one or more of the following temperatures for sedimentation: 15-20°C, 20-25°C, 25-30°C, 30-35°C, or 35-40°C.

[0075] For example, the temperature mentioned above is 15°C, 18°C, 20°C, 22°C, 25°C, 28°C, 30°C, 32°C, 35°C, 38°C, 40°C, or any value between the two mentioned above.

[0076] In some embodiments, the duration of the settling is one or more of the following: 20-30 min, 30-40 min, 40-50 min, 50-60 min, 60-70 min, or 70-80 min.

[0077] For example, the settlement duration is 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, 65 min, 70 min, 75 min, 80 min, or any value between the two above.

[0078] In some embodiments, the settling solution is selected from at least one of an aqueous methanol solution, an aqueous ethanol solution, an aqueous isopropanol solution, or an aqueous n-butanol solution.

[0079] For example, the settling solution includes an aqueous methanol solution.

[0080] For example, the sedimentation solution consists of an aqueous methanol solution of 90 wt%–95 wt%.

[0081] For example, the sedimentation solution includes an aqueous methanol solution with a concentration of 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, or any two of the above concentrations.

[0082] In some embodiments, the solid content of the resin polymer, based on the total mass of the resin-containing liquid composition and the acidic mixture, is one or more of the following: 3.0 wt%-3.5 wt%, 3.5 wt%-4.5 wt%, or 4.5 wt%-5.0 wt%.

[0083] For example, the solid content of the resin polymer is 3.0 wt%, 3.2 wt%, 3.3 wt%, 3.5 wt%, 3.8 wt%, 4.0 wt%, 4.2 wt%, 4.4 wt%, 4.5 wt%, 4.8 wt%, 5.0 wt%, or any value between the two.

[0084] In some embodiments of this application, a resin composition is provided, wherein the filtration time for preparing the resin composition is less than 1 minute; the resin composition includes resin and impurities, wherein the impurities are at least one selected from formic acid, acetic acid, oxalic acid, malonic acid, citric acid, tartaric acid, malic acid, lactic acid, gluconic acid, p-toluenesulfonic acid, trifluoroacetic acid, lactic acid, or benzoic acid; and the content of the impurities is greater than 0 and less than 100 ppb.

[0085] It should be noted that the acid content in the resin composition can be obtained by first dissolving the solid resin composition and then placing it in a measuring instrument.

[0086] For example, the impurity content in the resin composition can be 0.1 ppb, 1 ppb, 5 ppb, 10 ppb, 20 ppb, 30 ppb, 40 ppb, 50 ppb, 60 ppb, 70 ppb, 80 ppb, 90 ppb, 95 ppb, or any value between the two. The acid in the resin composition is, for example, one or more of the following: formic acid, acetic acid, oxalic acid, malonic acid, citric acid, tartaric acid, malic acid, lactic acid, gluconic acid, p-toluenesulfonic acid, trifluoroacetic acid, lactic acid, or benzoic acid.

[0087] In some embodiments of this application, a resin composition is provided, which is prepared by the method for preparing a resin composition as described in any of the above embodiments.

[0088] For example, the filtration time for preparing the resin composition is less than 1 minute. The resin composition includes resin and impurities, wherein the impurities are at least one selected from formic acid, acetic acid, oxalic acid, malonic acid, citric acid, tartaric acid, malic acid, lactic acid, gluconic acid, p-toluenesulfonic acid, trifluoroacetic acid, lactic acid, or benzoic acid. The impurity content is greater than 0 and less than 100 ppb.

[0089] In some embodiments of this application, a patterned composition is provided, comprising the resin composition described in any of the above embodiments and one or more of the following: a photosensitizer, a photoacid generator, or a solvent.

[0090] For example, the photosensitizers mentioned above include, but are not limited to, one or more of the following: diazonaphthoquinone sulfonate (DNQ), polyvinyl cinnamate, triphenyl sulfonate, triaryl sulfonate, or N-(trifluoromethylsulfonyloxy)phthalimide.

[0091] For example, the above-mentioned photoacid generators include, but are not limited to, one or more of triarylthionium salts, diaryliodothionium salts, or N-hydroxynaphthalimide trifluoromethanesulfonate.

[0092] For example, the solvents mentioned above include, but are not limited to, one or more of propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), ethyl lactate (EL), γ-butyrolactone (GBL), cyclohexanone (CYC), or diheptanone.

[0093] In some embodiments, the patterning composition further comprises one or more of a quencher, a surfactant / leveling agent, an adhesion promoter, or an antireflective substance.

[0094] For example, the quenching agents mentioned above include, but are not limited to, one or more of trioctylamine, tetrabutylammonium hydroxide (TBAH), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or N-tert-butoxycarbonyl-1,2,3,4-tetrahydroisoquinoline.

[0095] For example, the surfactants / leveling agents mentioned above include, but are not limited to, one or more of polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, or polyoxyethylene octylphenol ether.

[0096] For example, the adhesion promoters mentioned above include, but are not limited to, one or more of hexamethyldisilane (HMDS) or cobalt esters.

[0097] For example, the antireflective materials mentioned above include, but are not limited to, one or more of polymethacrylate, polyacrylate, polyimide, polysulfone or polyarylene ether.

[0098] In some embodiments of this application, a patterning method is provided, which includes: forming a pattern using a patterning composition according to any of the above embodiments; and performing one or more of cleaning, dehydration baking, thin film deposition, exposure, development, or ion implantation.

[0099] For example, the above cleaning includes, but is not limited to, one or more of wet cleaning or dry cleaning.

[0100] For example, the above-mentioned dehydration baking includes, but is not limited to, baking in one or more of a vacuum or nitrogen atmosphere.

[0101] For example, the above-mentioned thin film deposition includes, but is not limited to, one or more of chemical vapor deposition, physical vapor deposition, or atomic layer deposition.

[0102] For example, the above exposure includes, but is not limited to, one or more of optical exposure or particle beam exposure.

[0103] For example, the above-mentioned development includes, but is not limited to, one or more of immersion development or spray development.

[0104] For example, the ion implantation described above includes, but is not limited to, one or more of medium current implantation, high current implantation, or high energy implantation.

[0105] In some embodiments of this application, a semiconductor device is provided, the semiconductor device comprising a functional layer and an optional substrate, the functional layer being fabricated based on the patterned composition described in any of the above embodiments; the functional layer comprising one or more of a semiconductor layer, a conductive layer, or a dielectric layer.

[0106] It can be understood that the substrate serves as the base for supporting the device; the functional layer is a layer structure on the substrate that has a specific function (such as electrical, optical or chemical).

[0107] In some embodiments, the functional layer may include one or more of a semiconductor layer, a conductive layer, and a dielectric layer. The semiconductor layer is primarily used to form the active cells of a transistor, typically including an active region, polysilicon, or a semiconductor epitaxial layer. The conductive layer is used to form various conductive paths and electrode structures, typically including silicides, contact plugs, vias, metal gates, metal lines, pads, and metal barrier layers. The dielectric layer primarily serves to provide electrical isolation, dielectric support, and device protection, typically including shallow trench isolation dielectrics, gate dielectrics, gate sidewall dielectrics, contact layer dielectrics, inter-metal dielectrics, and top passivation dielectrics. The aforementioned semiconductor layer, conductive layer, and dielectric layer may be independent of each other or may be arranged in an alternating manner.

[0108] It is understood that the semiconductor device may be a wafer, an unpackaged or packaged chip, etc.

[0109] In some embodiments of this application, an electronic device is provided, the electronic device comprising: a circuit board; and the aforementioned semiconductor device, wherein the semiconductor device is electrically connected to the circuit board.

[0110] In some embodiments of this application, an electronic device is provided, the electronic device comprising: the above-described electronic device; and at least one of a power supply unit, an interconnection structure, a structural packaging component, and an input / output component.

[0111] In some implementations, the electronic device is, for example, a consumer electronic device, a home electronic appliance, an in-vehicle electronic device, a communication and network device, an industrial control device, a medical electronic device, a security and Internet of Things device, an office and financial device, an agricultural electronic device, an educational and scientific research electronic device, a new energy and energy storage system device, a robot and automated execution device, a rail transit and intelligent transportation system device, or an environmental protection and environmental monitoring device.

[0112] The technical solution of this application will be described in detail below with reference to specific embodiments. All substances used in the experiments are analytically pure and commercially available. Unless otherwise specified, all independent variable parameters defined in numerical or numerical range form in this specification are allowed a relative tolerance of ±5% due to fluctuations in conventional measurement accuracy and operating conditions, including ±3% instrument error. The relative tolerance means that, based on the specific numerical values ​​recorded in the embodiments, the absolute value of the deviation between the actual measured value and the reference value does not exceed 5% of the reference value, wherein the absolute value of the deviation between the instrument measured value and the reference value does not exceed 3% of the reference value.

[0113] Example Example 1 First, a trifluoroacetic acid (TFA) aqueous solution (1 g, 30 ppm) was added to a methanol aqueous solution (90 wt% methanol, 1749 g) as the sedimentation solution, and stirred until homogeneous, resulting in an acidic mixture with a pH of 3.62. At 20±2℃, a resin-containing liquid composition (250 g, 35 wt%) (the mass ratio of the resin-containing liquid composition to the acidic mixture was 1:7) was added dropwise to the acidic mixture (1750 g). After the addition was complete, the mixture was stirred at 30±5℃ and 218 rpm for 30–60 min to allow sedimentation. After sedimentation, the supernatant of the system was observed to be clear. The system was then cooled to room temperature and filtered. During filtration, the wet solid particles of the resin composition showed no adhesion, and there was no filter cloth clogging. Filtration was completed within 1 min. The settled resin composition was then subjected to an acid washing process, and the final resin composition contained <100 ppb of impurities. After sedimentation, the oligomer shearing rate of the resin composition was 7.5%, the monomer residue was 1.9 wt%, and the weight-average molecular weight increased by 5.3%.

[0114] Example 2 The acid solution was a 10 ppm aqueous solution of benzoic acid, and the pH of the acidic mixture was 4.42, otherwise consistent with Example 1. Results showed that after sedimentation, the supernatant of the system was clear, and the system after sedimentation was as described in Example 1. The settled system was cooled to room temperature and then filtered. During filtration, the wet solid particles of the resin composition did not adhere, and there was no filter cloth clogging; filtration was completed within 1 minute. The settled resin composition was subjected to an acid washing process, and the impurity content in the final resin composition was <100 ppb. The oligomer removal rate of the resin composition after sedimentation was 9.4%, the monomer residue was 0.05 wt%, and the weight-average molecular weight increased by 9.2%.

[0115] Example 3 The acid solution was a 250 ppm formic acid aqueous solution with a pH of 4.71, otherwise consistent with Example 1. Results showed that after sedimentation, the supernatant of the system was clear, and the system after sedimentation was as described in Example 1. The settled system was cooled to room temperature and then filtered. During filtration, the wet solid particles of the resin composition did not adhere, and there was no filter cloth clogging; filtration was completed within 1 minute. The settled resin composition was subjected to an acid washing process, and the final resin composition contained <100 ppb of impurities. The oligomer removal rate after sedimentation was 6.0%, the monomer residue was 1.8 wt%, and the weight-average molecular weight increased by 6.1%.

[0116] Example 4 The acid solution was a 500 ppm formic acid aqueous solution with a pH of 5.56, otherwise consistent with Example 1. Results showed that after sedimentation, the supernatant of the system was clear, and the system after sedimentation was as described in Example 1. The settled system was cooled to room temperature and then filtered. During filtration, the wet solid particles of the resin composition did not adhere, and there was no filter cloth clogging; filtration was completed within 1 minute. The settled resin composition was subjected to an acid washing process, and the impurity content in the final resin composition was <100 ppb. The oligomer removal rate of the resin composition after sedimentation was 6.9%, the monomer residue was 1.5 wt%, and the weight-average molecular weight increased by 6.1%.

[0117] Example 5 The acid solution was a 500 ppm aqueous solution of acetic acid, with a pH of 4.96, and the rest was consistent with Example 1. Results showed that after sedimentation, the supernatant of the system was clear, and the system after sedimentation was as described in Example 1. The settled system was cooled to room temperature and then filtered. During filtration, the wet solid particles of the resin composition did not adhere, and there was no filter cloth clogging; filtration was completed within 1 minute. The settled resin composition was subjected to an acid washing process, and the impurity content in the final resin composition was <100 ppb. The oligomer removal rate of the resin composition after sedimentation was 7.8%, the monomer residue was 1.3 wt%, and the weight-average molecular weight increased by 7.5%.

[0118] Example 6 The acid solution was a 600 ppm aqueous solution of lactic acid, and the pH of the acidic mixture was 4.82, otherwise consistent with Example 1. Results showed that after sedimentation, the supernatant of the system was clear, and the system after sedimentation was as described in Example 1. The settled system was cooled to room temperature and then filtered. During filtration, the wet solid particles of the resin composition did not adhere, and there was no filter cloth clogging; filtration was completed within 1 minute. The settled resin composition was subjected to an acid washing process, and the impurity content in the final resin composition was <100 ppb. The oligomer removal rate of the resin composition after sedimentation was 8.3%, the monomer residue was 0.9 wt%, and the weight-average molecular weight increased by 8.2%.

[0119] Example 7 The acid solution was a 35 ppm citric acid aqueous solution with a pH of 4.35, otherwise consistent with Example 1. Results showed that after sedimentation, the supernatant of the system was clear, and the system after sedimentation was as described in Example 1. The settled system was cooled to room temperature and then filtered. During filtration, the wet solid particles of the resin composition did not adhere, and there was no filter cloth clogging; filtration was completed within 1 minute. The settled resin composition was subjected to an acid washing process, and the final resin composition contained <100 ppb of impurities. The oligomer removal rate after sedimentation was 8.9%, the monomer residue was 0.5 wt%, and the weight-average molecular weight increased by 8.5%.

[0120] Example 8 The acid solution was a 200 ppm aqueous solution of oxalic acid, and the pH of the acidic mixture was 4.07; the rest was consistent with Example 1. The results showed that sedimentation was observed after the sedimentation process (e.g., Figure 1 As shown in Example 1), the supernatant of the settled system was clear. The settled system was cooled to room temperature and then filtered. During filtration, the wet solid particles of the resin composition did not stick together, and there was no filter cloth clogging. The filtration was completed within 1 minute. The settled resin composition was subjected to an acid washing process, and the impurity content in the final resin composition was <100 ppb. The oligomer removal rate of the resin composition after sedimentation was 5.3%, the monomer residue was 1.8 wt%, and the weight-average molecular weight increased by 5.6%.

[0121] Example 9 The acid solution was a 2 ppm aqueous solution of benzoic acid, and the pH of the acidic mixture was 5.45, otherwise consistent with Example 1. Results showed that after sedimentation, the supernatant of the system was clear, and the system after sedimentation was as described in Example 1. The settled system was cooled to room temperature and then filtered. During filtration, the wet solid particles of the resin composition did not adhere, and there was no filter cloth clogging; filtration was completed within 1 minute. The settled resin composition was subjected to an acid washing process, and the impurity content in the final resin composition was <100 ppb. The oligomer removal rate of the resin composition after sedimentation was 9.7%, the monomer residue was 0.04 wt%, and the weight-average molecular weight increased by 9.5%.

[0122] Example 10 The mass ratio of the resin-containing liquid composition to the acidic mixture was 1:9, and the pH of the acidic mixture was 4.36, otherwise consistent with Example 2. Results showed that after sedimentation, the supernatant of the system was clear, and the system after sedimentation was as described in Example 1. The settled system was cooled to room temperature and then filtered. During filtration, the wet solid particles of the resin composition did not adhere, and there was no filter cloth clogging; filtration was completed within 1 minute. The settled resin composition was subjected to an acid washing process, and the impurity content in the final resin composition was <100 ppb. The oligomer removal rate of the resin composition after sedimentation was 9.5%, the monomer residue was 0.1 wt%, and the weight-average molecular weight increased by 8.6%.

[0123] Example 11 The sedimentation solution was 20 kg, and the pH of the acidic mixture was 4.43, otherwise consistent with Example 2. Results showed that after sedimentation, the supernatant of the system was clear, and the system after sedimentation was similar to that in Example 1. The sedimented system was cooled to room temperature and then filtered. During filtration, the wet solid particles of the resin composition did not adhere, and there was no filter cloth clogging; filtration was completed within 1 minute. The sedimented resin composition was subjected to an acid washing process, and the impurity content in the final resin composition was <100 ppb. The oligomer removal rate of the resin composition after sedimentation was 9.8%, the monomer residue was 0.5 wt%, and the weight-average molecular weight increased by 8.9%.

[0124] Comparative Example Comparative Example 1 Comparative Example 1: First, a methanol-water solution (90 wt% methanol, 1750 g) was stirred until homogeneous to obtain a sedimentation solution with a pH of 6.91. At 20±2℃, a resin-containing liquid composition (250 g, 35 wt%) (the mass ratio of the resin-containing liquid composition to the sedimentation solution was 1:7) was added dropwise to the sedimentation solution (1750 g). After the addition was complete, the mixture was stirred at 30±5℃ and 218 rpm for 30–60 min to allow sedimentation. The system after sedimentation was as follows: Figure 2As shown, during the filtration of the settled system, the wet solid particles of the resin composition agglomerate and clog the filter cloth, making filtration difficult. After sedimentation, the oligomer removal rate of the resin composition was 2.3%, the monomer residue was 3.2 wt%, and the weight-average molecular weight increased by 2.0%.

[0125] Comparative Example 2 A sodium bicarbonate aqueous solution (1 g, 20 ppm) was added to the sedimentation solution and stirred until homogeneous, yielding a mixture with a pH of 12.2. The remaining parameters were consistent with Comparative Example 1. The results showed that after sedimentation, the system exhibited the following characteristics: Figure 3 As shown, during the filtration of the settled system, the wet solid particles of the resin composition agglomerate and clog the filter cloth, making filtration difficult. After sedimentation, the oligomer removal rate of the resin composition was 3.2%, the monomer residue was 2.5 wt%, and the weight-average molecular weight increased by 2.2%.

[0126] Comparative Example 3 The mass ratio of the resin-containing liquid composition to the sedimentation solution was 1:10, with the remaining parameters consistent with Comparative Example 1. The results showed that after sedimentation, the system resembled that of Comparative Example 1. During filtration of the sedimented system, the wet solid particles of the resin composition agglomerated, clogging the filter cloth and making filtration difficult. After sedimentation, the oligomer removal rate of the resin composition was 3.9%, the monomer residue was 3.0 wt%, and the weight-average molecular weight increased by 3.5%.

[0127] Comparative Example 4 The stirring speed was reduced to 139 rpm, while the rest remained the same as in Comparative Example 1. The results showed that after sedimentation, the system resembled that of Comparative Example 1. During filtration of the settled system, the wet solid particles of the resin composition agglomerated, clogging the filter cloth and making filtration difficult. After sedimentation, the oligomer removal rate of the resin composition was 4.2%, the monomer residue was 3.2 wt%, and the weight-average molecular weight increased by 4.3%.

[0128] Comparative Example 5 The sedimentation solution was an aqueous methanol solution (95 wt% methanol, 2500 g), with the remainder consistent with Comparative Example 3. The results showed that after sedimentation, the system resembled that of Comparative Example 1. During filtration of the sedimented system, the wet solid particles of the resin composition agglomerated, clogging the filter cloth and making filtration difficult. After sedimentation, the oligomer removal rate of the resin composition was 4.8%, the monomer residue was 2.9 wt%, and the weight-average molecular weight increased by 4.8%.

[0129] By comparing the above embodiments with comparative examples, it can be seen that the method of this disclosure enables the resin composition to exhibit a normal physical state without resin adhesion during the sedimentation process, solving the problem of resin composition clogging during filtration. This significantly shortens the production cycle, reduces costs, and improves the overall process stability and economy. Furthermore, the resin composition purified by the method of this application shows a more significant increase in weight-average molecular weight and a more pronounced decrease in PDI before and after purification. For example, after purification, the weight-average molecular weight of the resin composition increases from 6500 Da to 7500 Da, and the PDI decreases from 1.9 to 1.59.

[0130] The above description merely illustrates exemplary embodiments of this application, and while the description is specific and detailed, it should not be construed as limiting the scope of this application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these modifications and improvements all fall within the protection scope of this application.

[0131] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone, where A and B can be singular or plural. The character " / " generally indicates that the related objects before and after it are in an "or" relationship.

[0132] It should be noted that, in the case shown in claim 7, each semicolon can be considered a unit. For example, "the concentration of the acid solution is one or more of the following: 2-100 ppm, 100-500 ppm, or 500-600 ppm", "the sedimentation includes adding the resin-containing liquid composition dropwise to the acidic mixture at one or more of the following temperatures for sedimentation: 15-20°C, 20-25°C, 25-30°C, 30-35°C, or 35-40°C", and "the sedimentation duration is one or more of the following: 20-30 min, 30-40 min, 40-50 min, 50-60 min, 60-70 min, or 70-80 min", etc., are all units. The appearance of 'and / or' between each unit indicates that there is an 'and / or' relationship between the units.

[0133] For example, the concentration of the acid solution is one or more of the following: 2-100 ppm, 100-500 ppm, or 500-600 ppm; and / or, the sedimentation includes adding the resin-containing liquid composition dropwise to the acidic mixture at one or more of the following temperatures for sedimentation: 15-20°C, 20-25°C, 25-30°C, 30-35°C, or 35-40°C; which can be understood as the following three cases: Scenario 1: The concentration of the acid solution is one or more of the following: 2-100 ppm, 100-500 ppm, or 500-600 ppm; and the sedimentation includes adding the resin-containing liquid composition dropwise to the acidic mixture at one or more of the following temperatures for sedimentation: 15-20°C, 20-25°C, 25-30°C, 30-35°C, or 35-40°C; Scenario 2: The concentration of the acid solution is one or more of the following: 2-100 ppm, 100-500 ppm, or 500-600 ppm; Case 3: The sedimentation includes adding the resin-containing liquid composition dropwise to the acidic mixture at one or more of the following temperatures for sedimentation: 15-20°C, 20-25°C, 25-30°C, 30-35°C, or 35-40°C.

[0134] In the description of this application, unless otherwise stated, "multiple" means two or more. "At least one" means one or more. "At least one of the following," "one or more of the following," or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c," "one or more of a, b, or c," "at least one of a, b, and c," or "one or more of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0135] In this application, the numerical range indicated by "-" refers to the range including the minimum and maximum values ​​recorded before and after "-", respectively. For example, the value of 'a' can be 0.5-15, meaning that the value of 'a' can be between 0.5 and 15, including the endpoints 0.5 and 15. Expressions of parameter ranges in this application, such as "greater than or equal to (≥)", "less than or equal to (≤)", "above", and "below", all include the stated number. The numerical values ​​and ranges involved in the embodiments of this application are approximate values ​​and may have a certain range of errors due to the influence of manufacturing processes / testing methods, etc., and this part of the error is also within the scope of protection of this application.

Claims

1. A method for preparing a resin composition, characterized in that, The method includes: An acidic mixture is obtained by mixing the acid solution with the sedimentation solution; The resin-containing liquid composition is precipitated in the acidic mixture to purify the resin-containing liquid composition and obtain a purified resin composition. Compared to the resin-containing liquid composition, the purified resin composition has an oligomer cleavage rate of 5%-10% and an increase in weight-average molecular weight of 5.2%-9.2%. The pH value of the acidic mixture is 3-6, and the mass ratio of the resin-containing liquid composition to the acidic mixture is 1:6-1:

10. The acid in the acid solution is an organic acid, which is selected from one or more of the following: formic acid, acetic acid, oxalic acid, malonic acid, citric acid, tartaric acid, malic acid, lactic acid, gluconic acid, p-toluenesulfonic acid, trifluoroacetic acid, lactic acid, or benzoic acid. The settling solution includes one or more of the following: an aqueous alcohol solution, an alkane solution, or an ether solution.

2. The method according to claim 1, characterized in that, The settling solution is selected from an alcohol-water solution.

3. The method according to claim 1 or 2, characterized in that, Based on the total mass of the purified resin composition, the residual monomer content of the purified resin composition is 0.01 wt%-2.00 wt%.

4. The method according to any one of claims 1-3, characterized in that, The concentration of the acid solution is 2-600 ppm.

5. The method according to any one of claims 1-4, characterized in that, The resin-containing liquid composition comprises a resin polymer, and the solid content of the resin polymer, based on the total mass of the resin-containing liquid composition, is one or more of the following: 30 wt%-35 wt%, 35 wt%-45 wt%, or 45 wt%-50 wt%.

6. The method according to any one of claims 1-5, characterized in that, The method also includes vacuum filtration, the vacuum filtration being completed in less than 1 minute.

7. The method according to claim 5, characterized in that, The concentration of the acid solution is one or more of the following: 2-100 ppm, 100-500 ppm, or 500-600 ppm; And / or, the sedimentation includes adding the resin-containing liquid composition dropwise to the acidic mixture at one or more of the following temperatures for sedimentation: 15-20°C, 20-25°C, 25-30°C, 30-35°C, or 35-40°C; And / or, the duration of the settlement is one or more of the following: 20-30 min, 30-40 min, 40-50 min, 50-60 min, 60-70 min, or 70-80 min; And / or, the settling solution is selected from at least one of methanol aqueous solution, ethanol aqueous solution, isopropanol aqueous solution or n-butanol aqueous solution; And / or, based on the total mass of the resin-containing liquid composition and the acidic mixture, the solid content of the resin polymer is one or more of the following: 3.0 wt%-3.5 wt%, 3.5 wt%-4.5 wt%, or 4.5 wt%-5.0 wt%.

8. A resin composition, characterized in that, The filtration time for preparing the resin composition is less than 1 minute; The resin composition includes a resin and an impurity, wherein the impurity is at least one selected from formic acid, acetic acid, oxalic acid, malonic acid, citric acid, tartaric acid, malic acid, lactic acid, gluconic acid, p-toluenesulfonic acid, trifluoroacetic acid, lactic acid, or benzoic acid. The content of the impurity is greater than 0 and less than 100 ppb.

9. A patterned composition, characterized in that, The patterned composition comprises the resin composition of claim 8 and one or more of the following: a photosensitizer, a photoacid generator, or a solvent.

10. A patterning method, characterized in that, The patterning method includes: Forming a pattern using the patterning composition of claim 9; and Perform one or more of the following: cleaning, dehydration and baking, thin film deposition, exposure, development, or ion implantation.

11. A semiconductor device, characterized in that, The semiconductor device includes a functional layer and an optional substrate, the functional layer being fabricated based on the patterned composition of claim 9; the functional layer includes one or more of a semiconductor layer, a conductive layer, or a dielectric layer.

12. An electronic device, characterized in that, The electronic device includes: Circuit boards; and The semiconductor device according to claim 11, wherein the semiconductor device is electrically connected to the circuit board.

13. An electronic device, characterized in that, The electronic device includes: The electronic device according to claim 12; and At least one of a power supply unit, an interconnection structure, a structural packaging component, and an input / output component.

14. The electronic device according to claim 13, characterized in that, The electronic devices are selected from: consumer electronic devices, home electronic appliances, vehicle electronic devices, communication and network equipment, industrial control equipment, medical electronic devices, security and Internet of Things equipment, office and financial equipment, agricultural electronic devices, educational and scientific research electronic devices, new energy and energy storage system equipment, robotics and automated execution equipment, rail transit and intelligent transportation system equipment, or environmental protection and environmental monitoring equipment.

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