Platinum (II) complex-based chemical amplification photoresist and application thereof

Abstract

The invention provides a chemical amplification photoresist based on a platinum (II) complex and application of the chemical amplification photoresist. The chemical amplification photoresist comprises polymer resin containing a protecting group, a photoacid generator, an acid quenching agent and a solvent, wherein the photoacid generator comprises a first photoacid generator, and the first photoacid generator comprises at least one platinum (II) complex. According to the invention, the platinum (II) complex is introduced as the first photoacid generator, sufficient effective acid can be generated in a slightly alkaline environment or an environment rich in dangling bonds, and the photoacid generation efficiency after exposure is obviously higher than that of a traditional photoacid generator, so that a deprotection reaction can be fully completed at the bottom of an exposure area of the photoresist, and the yield of the photoresist is improved. And the formation of residues or bottom feet can be effectively inhibited, and a photoetching pattern with high resolution and good morphology can be obtained.

Description

Technical Field

[0001] This invention relates to the field of photolithography, and in particular to a chemically amplified photoresist based on platinum(II) complexes and its applications. Background Technology

[0002] When processing semiconductor materials on their surfaces, the desired image can be obtained by using appropriate and selective photoresists. Chemically amplified photoresists are a commonly used type of photoresist. Their main components include poly(p-hydroxystyrene) resin with protecting groups, a photoacid generator (PAG), an acid quencher, additives, and a solvent. The main principle of this type of photoresist is that the photoacid generator absorbs light energy to produce acid, which catalyzes a deprotection reaction in the resin, transforming the resin in the exposed area from insoluble in the developer to soluble in it. In this process, the acid acts as a catalyst and is not consumed, thus amplifying the light signal into a chemical signal. This is why this type of photoresist is called a chemically amplified photoresist.

[0003] However, in practical applications, the total effective acid generated by the photoacid generator in traditional chemically amplified photoresists is insufficient, directly affecting the degree and efficiency of the deprotection reaction within the photoresist. Especially when the substrate surface has a slightly alkaline or dangling bond-rich thin film layer (e.g., Si3N4 film), some of the acid generated at the bottom of the photoresist exposure area reacts with the substrate surface material, reducing the available acid amount and thus weakening the expected deprotection effect. After development, this reduced acid concentration leads to the formation of residues or traces at the bottom of the photoresist exposure area, severely affecting the resolution and morphology of the lithographic pattern. Summary of the Invention

[0004] The purpose of this invention is to provide a chemically amplified photoresist based on platinum(II) complexes and its application, in order to solve one or more of the problems existing in the prior art, such as insufficient effective acid generated by the photoacid generator in traditional chemically amplified photoresists, which affects the resolution and morphology of the photolithographic pattern.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solution: a chemically amplified photoresist based on a platinum(II) complex, comprising: a polymer resin containing a protecting group, a photoacid generator, an acid quencher, and a solvent; wherein the photoacid generator comprises a first photoacid generator, and the first photoacid generator comprises at least one platinum(II) complex.

[0006] Optionally, the chemically amplified photoresist further includes additives, which include at least one of a dissolution inhibitor, a surfactant, and a stabilizer; in the chemically amplified photoresist, by weight percentage, the polymer resin containing a protecting group is 1% to 20%, the photoacid generator is 0.2% to 5%, the first photoacid generator is 0.1% to 2%, the acid quencher is 0.1% to 2%, the solvent is 75% to 98%, and the dissolution inhibitor, the surfactant, and the stabilizer are all 0% to 0.3%.

[0007] Optionally, the platinum(II) complex includes a platinum(II)-bipyridine sulfonic acid complex;

[0008] The molecular formula of the platinum(II)-bipyridine sulfonic acid complex is:

[0009]

[0010] Where A is a molecular formula C a F 2a+1 Perfluoroalkyl, where a is an integer from 1 to 10; R is hydrogen or has the molecular formula C b H 2b+1 Alkyl groups, where b is an integer from 1 to 20.

[0011] Optionally, the photoacid generator further includes a second photoacid generator, which includes at least one of thioonium salt photoacid generators, iodonium salt photoacid generators, and sulfonate salt photoacid generators.

[0012] Optionally, the polymer resin containing the protecting group includes at least one of p-hydroxystyrene polymers containing the protecting group and acrylate polymers containing the protecting group.

[0013] Optionally, the acid quencher includes basic amine compounds or weak acid onium salts.

[0014] Optionally, the solvent includes at least one selected from propylene glycol methyl ether acetate, ethyl lactate, γ-butyrolactone, amyl acetate, methyl butyl acetate, propylene glycol methyl ether, propylene glycol ethyl ether, anisole, 2-heptanone, cyclohexanone, and cyclopentanone.

[0015] To achieve the above objectives, the present invention also provides a method for preparing a chemically amplified photoresist based on a platinum(II) complex as described in any of the preceding claims, the method comprising:

[0016] The following components are weighed according to a preset ratio: a polymer resin containing a protecting group, a photoacid generator, an acid quencher, a dissolution inhibitor, a surfactant, and a solvent; wherein the photoacid generator includes a first photoacid generator, which includes at least one platinum(II) complex.

[0017] The obtained solvent, the polymer resin containing the protective group, the dissolution inhibitor, the photoacid generator, the acid quencher, and the surfactant are sequentially added to a mixing container for mixing to obtain the chemically amplified photoresist.

[0018] Optionally, the preset ratio includes, by weight percentage, 1% to 20% of the polymer resin containing the protective group, 0.2% to 5% of the photoacid generator, 0.1% to 2% of the first photoacid generator, 0.1% to 2% of the acid quencher, 75% to 98% of the solvent, and 0% to 0.3% of both the dissolution inhibitor and the surfactant.

[0019] To achieve the above objectives, the present invention also provides a method for using a platinum(II) complex-based chemically amplified photoresist as described in any of the preceding claims, the method comprising:

[0020] A silicon wafer is provided, wherein the surface of the silicon wafer is provided with a thin film layer that is slightly alkaline or rich in dangling bonds;

[0021] The platinum(II) complex-based chemical amplification photoresist described in any of the above-mentioned methods is coated on the silicon wafer, and the photolithographic pattern is obtained by pre-baking, exposure, post-baking and development.

[0022] Compared with the prior art, the chemically amplified photoresist based on platinum(II) complexes and its application provided by the present invention have the following beneficial effects:

[0023] The present invention provides a chemically amplified photoresist based on platinum(II) complexes, comprising: a polymer resin containing a protecting group, a photoacid generator, an acid quencher, and a solvent; wherein the photoacid generator includes a first photoacid generator, which includes at least one platinum(II) complex. Therefore, the chemically amplified photoresist based on platinum(II) complexes provided by the present invention, by introducing a platinum(II) complex as the first photoacid generator, allows alkaline substances on the substrate surface to undergo ligand exchange with sulfonate ligands in the platinum(II) complex before exposure in a slightly alkaline or dangling bond-rich environment, forming a highly active hydroxyl intermediate; this intermediate efficiently dissociates under light irradiation, simultaneously releasing sulfonate anions and highly active hydroxyl radicals; these hydroxyl radicals initiate a chain reaction in the organic-rich photoresist environment, generating a large number of extra protons (H). +This results in a final effective acid quantity exceeding the initial number of coordinated sulfonate ligands, thus significantly increasing the photoacid generation efficiency after exposure compared to traditional photoacid generators. Furthermore, when the platinum(II) complex-based chemically amplified photoresist provided by this invention is used on a substrate with a slightly alkaline or dangling bond-rich thin film layer, it can generate sufficient effective acid. Even if some of the initial acid reacts with the substrate surface material, the protons (H+) generated in the chain reaction... + This method still ensures that the bottom of the photoresist exposure area fully completes the deprotection reaction, thereby effectively suppressing the formation of residues or traces and obtaining high-resolution photolithographic patterns with good morphology. Furthermore, using the platinum(II) complex-based chemically amplified photoresist provided by this invention eliminates the need for additional surface modification or anti-reflective coating processes, not only avoiding potential damage to the substrate but also simplifying the manufacturing process and reducing process complexity and cost.

[0024] Since the preparation method and usage method of the platinum(II) complex-based chemical amplification photoresist provided by this invention belong to the same inventive concept as the platinum(II) complex-based chemical amplification photoresist provided by this invention, they at least possess all the advantages of the platinum(II) complex-based chemical amplification photoresist provided by this invention. For details regarding the advantages of the preparation method and usage method of the platinum(II) complex-based chemical amplification photoresist provided by this invention, please refer to the relevant description of the beneficial effects of the platinum(II) complex-based chemical amplification photoresist provided by this invention; further details will not be repeated here. Attached Figure Description

[0025] Figure 1 This is a schematic diagram illustrating the mechanism of a chemically amplified photoresist based on a platinum(II) complex acting on a substrate, as provided in Embodiment 1 of the present invention.

[0026] Figure 2 SEM image of a photolithographic pattern formed after a platinum(II) complex-based chemically amplified photoresist is applied to a substrate, as provided in Embodiment 1 of the present invention;

[0027] Figure 3 This is a schematic flowchart of a method for preparing a chemically amplified photoresist based on a platinum(II) complex, as provided in Embodiment 2 of the present invention.

[0028] The annotations in the attached figures are explained as follows:

[0029] 100 - Substrate, 210 - Chemically amplified photoresist based on platinum(II) complex, 211 - Photoresist exposure area. Detailed Implementation

[0030] The following detailed description, in conjunction with the accompanying drawings and specific embodiments, further illustrates the platinum(II) complex-based chemically amplified photoresist and its applications proposed in this invention. The advantages and features of this invention will become clearer from the following description. It should be noted that the drawings are all in a very simplified form and use non-precise proportions, used only to facilitate and clarify the illustration of the embodiments of this invention. Please refer to the drawings to make the objectives, features, and advantages of this invention more apparent and understandable. It should be understood that the structures, proportions, sizes, etc., depicted in the accompanying drawings are only for illustrative purposes and to enable those skilled in the art to understand and read them, and are not intended to limit the implementation conditions of this invention. Any modifications to the structure, changes in proportions, or adjustments to the size, provided that the effects and objectives achieved by this invention are the same or similar, should still fall within the scope of the technical content disclosed in this invention. Specific design features of the invention disclosed herein, including, for example, specific dimensions, orientations, positions, and shapes, will be determined in part by the specific application and environment in which they are used. Furthermore, in the embodiments described below, the same reference numerals are sometimes used in different figures to denote the same parts or parts with the same function, and repeated descriptions are omitted.

[0031] Example 1

[0032] This embodiment provides a chemically amplified photoresist based on a platinum(II) complex. Specifically, the platinum(II) complex-based chemically amplified photoresist comprises: a polymer resin containing a protecting group, a photoacid generator, an acid quencher, and a solvent; wherein the photoacid generator includes a first photoacid generator, which includes at least one platinum(II) complex. Therefore, the platinum(II) complex-based chemically amplified photoresist provided in this embodiment, by introducing a platinum(II) complex as the first photoacid generator, allows alkaline substances on the substrate surface to undergo ligand exchange with sulfonate ligands in the platinum(II) complex before exposure in a slightly alkaline or dangling bond-rich environment, forming a highly active hydroxyl intermediate. This intermediate efficiently dissociates under light irradiation, simultaneously releasing sulfonate anions and highly active hydroxyl radicals. These hydroxyl radicals initiate a chain reaction in the organic-rich photoresist environment, generating a large number of extra protons (H). + This results in a final effective total acid amount exceeding the number of initially coordinated sulfonate ligands, thus making the photoacid generation efficiency after exposure significantly higher than that of traditional photoacid generators.

[0033] For example, please see Figure 1 and Figure 2 , Figure 1 This is a schematic diagram illustrating the mechanism of the chemically amplified photoresist 210 based on platinum(II) complex acting on the substrate 100 in this embodiment. Figure 2 This is a SEM image of the photolithographic pattern formed by the platinum(II) complex-based chemically amplified photoresist 210 after being applied to the substrate 100, as provided in this embodiment; wherein, Figure 2 The SEM images shown were obtained using scanning electron microscopy (SEM). Figure 1 It can be seen that when the platinum(II) complex-based chemical amplification photoresist 210 provided in this embodiment is used on a substrate 100 with a thin film layer that is slightly alkaline or rich in dangling bonds, it can generate a sufficient amount of effective acid. Even if some of the initial acid reacts with the surface material of the substrate 100, the protons (H+) generated by the chain reaction will be effectively produced. + This still ensures that the bottom of the photoresist exposure area 211 fully completes the deprotection reaction, thereby effectively suppressing the formation of residues or traces and obtaining high-resolution photolithographic patterns with good morphology (such as...). Figure 2 (As shown). Furthermore, by using the platinum(II) complex-based chemical amplification photoresist 210 provided in this embodiment, no additional surface modification or anti-reflection coating process is required. This not only avoids potential damage to the substrate 100 but also simplifies the manufacturing process and reduces process complexity and cost.

[0034] Preferably, in some embodiments, the platinum(II) complex-based chemical amplification photoresist 210 further includes additives, the additives including at least one of a dissolution inhibitor, a surfactant, and a stabilizer; in the platinum(II) complex-based chemical amplification photoresist 210, by weight percentage, the polymer resin containing the protecting group is 1% to 20%, the photoacid generator is 0.2% to 5%, the first photoacid generator is 0.1% to 2%, the acid quencher is 0.1% to 2%, the solvent is 75% to 98%, and the dissolution inhibitor, the surfactant, and the stabilizer are all 0% to 0.3%.

[0035] For example, in some embodiments, the platinum(II) complex-based chemical amplification photoresist 210 may not contain the stabilizer (i.e., the stabilizer content is 0%); in other embodiments, the platinum(II) complex-based chemical amplification photoresist 210 may also contain the dissolution inhibitor, the surfactant, and the stabilizer, all of which are present at a content of 0.1%.

[0036] Exemplarily, in some embodiments, the platinum(II) complex comprises a platinum(II)-bipyridine sulfonic acid complex;

[0037] The molecular formula of the platinum(II)-bipyridine sulfonic acid complex is:

[0038]

[0039] Where A is a molecular formula C a F 2a+1 Perfluoroalkyl, where a is an integer from 1 to 10; R is hydrogen or has the molecular formula C b H 2b+1 Alkyl groups, where b is an integer from 1 to 20.

[0040] To facilitate understanding of the present invention, the mechanism by which the platinum(II)-bipyridine sulfonic acid complex, when used as the first photoacid generator, significantly improves the photoacid generation efficiency after exposure compared to conventional photoacid generators in alkaline or dangling bond-rich environments is briefly explained below.

[0041] First, the pre-activation process: alkaline substances (such as OH-) - Before exposure, it replaces a sulfonate ligand to form a highly active intermediate [Pt(bpy)(OH)(OSO2R)] (where bpy is a bipyridine ligand). Then, a synergistic photodissociation process occurs: under light irradiation, this intermediate dissociates efficiently, releasing the sulfonate anion (RSO3). - ) and highly reactive hydroxyl radicals. Hydroxyl radicals initiate a chain reaction in the organic-rich photoresist environment, a process that generates a large number of extra protons (H). + This results in the final effective total acid amount far exceeding the number of initially coordinated sulfonate ligands.

[0042] It should be noted that the present invention does not impose excessive limitations on the preparation method of the platinum(II)-bipyridine sulfonic acid complex. Exemplarily, in some embodiments, in the molecular formula of the platinum(II)-bipyridine sulfonic acid complex, R is hydrogen and A is perfluorobutyl (C4F9), that is, when the platinum(II)-bipyridine sulfonic acid complex is a platinum(II)-bipyridine-perfluorobutyl sulfonic acid complex, its preparation steps can be as follows: First, under nitrogen protection and light-protected conditions, equimolar amounts of potassium chloroplatinate (K2PtCl4) and 2,2... 'Bipyridine was dissolved in a mixed solvent of deionized water and ethanol, and the mixture was heated to 70°C-80°C and stirred for 12-24 hours. After the reaction was completed, it was cooled to room temperature, and a yellow solid precipitated. The yellow solid was collected by vacuum filtration and washed successively with cold water, a small amount of ethanol, and diethyl ether, and then dried under vacuum to obtain a yellow powder intermediate for later use. Then, equimolar amounts of perfluorobutylsulfonic acid and silver nitrate were dissolved in a small amount of deionized water to obtain sulfonic acid solution and silver nitrate solution, respectively. Under light-protected conditions, the silver nitrate solution was added dropwise to the sulfonic acid solution, and a white precipitate was immediately formed. After the addition was completed, the mixture was stirred for 1 hour to ensure the reaction was complete. The white precipitate was collected by vacuum filtration and washed with a large amount of deionized water until the filtrate was neutral. Then, it was dried in a vacuum desiccator under light to obtain a white precipitate intermediate for later use. Next, the yellow powder intermediate (identified as (2,2) ' Platinum(II) dichlorobispyridine (Bipyridine) and the white precipitate intermediate (identified as silver perfluorobutylsulfonate) were added in a dry polar aprotic solvent (such as acetonitrile or acetone) at a molar ratio of 1:2. Under nitrogen protection, the reaction mixture was heated to reflux (e.g., approximately 82°C when using acetonitrile as the solvent) and stirred in the dark for 24–48 hours. After the reaction was complete, the silver chloride precipitate was removed by hot filtration. The resulting filtrate was then concentrated to approximately one-third of its original volume by rotary evaporation under reduced pressure. Finally, the concentrated solution was slowly added dropwise to vigorously stirred diethyl ether or n-hexane to precipitate the target product (which typically precipitates as a solid). The target product was collected, washed several times with diethyl ether, and dried under high vacuum to obtain the platinum(II)-bipyridine-perfluorobutylsulfonate complex.

[0043] Preferably, in some embodiments, the photoacid generator further includes a second photoacid generator, which includes at least one of a thioonium salt photoacid generator, an iodonium salt photoacid generator, and a sulfonate photoacid generator. Thus, by adding a common second photoacid generator, the photoacid generation efficiency can be further improved.

[0044] Exemplarily, in some embodiments, the polymer resin containing a protecting group includes at least one of a p-hydroxystyrene polymer containing a protecting group and an acrylate polymer containing a protecting group.

[0045] Exemplarily, in some embodiments, the acid quencher includes basic amine compounds or weak acid onium salts.

[0046] Exemplary examples, in some embodiments, the solvent includes at least one selected from propylene glycol methyl ether acetate, ethyl lactate, γ-butyrolactone, amyl acetate, methyl butyl acetate, propylene glycol methyl ether, propylene glycol ethyl ether, anisole, 2-heptanone, cyclohexanone, and cyclopentanone.

[0047] To better understand the present invention, the components and weight percentages of a chemically amplified photoresist 210 based on a platinum (II) complex provided in this embodiment are illustrated below by way of example.

[0048] The platinum(II) complex-based chemically amplified photoresist 210 comprises: 5% of a polymer resin containing protecting groups (in which the main chain is a p-hydroxystyrene polymer and the side chain is incorporating tert-butyloxycarbonyl protecting groups), 1% of a first photoacid generator (the first photoacid generator is a platinum(II)-bipyridine-perfluorobutylsulfonic acid complex), 0.5% of a second photoacid generator (the second photoacid generator is triphenylthionium trifluoromethanesulfonate, belonging to the thionium salt class of photoacid generators), 0.3% of an acid quencher (the acid quencher is triethanolamine, belonging to the basic amine compound class), 0.2% of a dissolution inhibitor (the dissolution inhibitor is a bisphenol A type dissolution inhibitor), 0.1% of a surfactant (the surfactant is a fluorocarbon surfactant, model FC-4430), and 92.1% of a solvent (the solvent is a mixture of propylene glycol methyl ether acetate and propylene glycol ethyl ether in a volume ratio of 1:1).

[0049] Example 2

[0050] This embodiment provides a method for preparing a chemically amplified photoresist based on a platinum(II) complex, wherein the chemically amplified photoresist is the platinum(II) complex-based chemically amplified photoresist described in any of the above embodiments. Specifically, please refer to... Figure 3 , Figure 3 This is a schematic flowchart illustrating the preparation method of the platinum(II) complex-based chemically amplified photoresist provided in this embodiment. From... Figure 3 It can be seen that the preparation method includes:

[0051] S100: Weigh out the polymer resin containing the protecting group, the photoacid generator, the acid quencher, the dissolution inhibitor, the surfactant, and the solvent according to the preset ratio; wherein, the photoacid generator includes a first photoacid generator, and the first photoacid generator includes at least one platinum(II) complex;

[0052] S200: The obtained solvent, the polymer resin containing the protective group, the dissolution inhibitor, the photoacid generator, the acid quencher, and the surfactant are sequentially added to a mixing container for mixing to obtain the chemically amplified photoresist based on the platinum(II) complex.

[0053] For example, in some embodiments, the preset ratio includes, by weight percentage, 1% to 20% of the polymer resin containing the protective group, 0.2% to 5% of the photoacid generator, 0.1% to 2% of the first photoacid generator, 0.1% to 2% of the acid quencher, 75% to 98% of the solvent, and 0% to 0.3% of both the dissolution inhibitor and the surfactant.

[0054] Since the preparation method of the platinum(II) complex-based chemical amplification photoresist provided in this embodiment belongs to the same inventive concept as the platinum(II) complex-based chemical amplification photoresist provided in any of the above embodiments, the preparation method of the platinum(II) complex-based chemical amplification photoresist provided in this embodiment has at least all the advantages of the platinum(II) complex-based chemical amplification photoresist provided in the above embodiments. For the advantages of the preparation method of the platinum(II) complex-based chemical amplification photoresist provided in this embodiment, please refer to the relevant description of the beneficial effects of the platinum(II) complex-based chemical amplification photoresist provided in the above embodiments, which will not be repeated here.

[0055] To facilitate understanding of the present invention, the specific process of the preparation method of the chemically amplified photoresist based on platinum(II) complex provided in this embodiment is illustrated below by way of example.

[0056] First, weigh the following components by weight percentage: 5% of a polymer resin containing a protecting group (in which the main chain is a p-hydroxystyrene polymer and the side chain is introduced with a tert-butyloxycarbonyl protecting group), a photoacid generator (including 1% of a platinum(II)-bipyridine-perfluorobutylsulfonic acid complex and 0.5% of triphenylthionium trifluoromethanesulfonate), 0.3% of an acid quencher (the acid quencher is triethanolamine, which belongs to the basic amine compound), 0.2% of a dissolution inhibitor (the dissolution inhibitor is a bisphenol A type dissolution inhibitor), 0.1% of a surfactant (the surfactant is a fluorocarbon surfactant, model FC-4430), and 92.1% of a solvent (the solvent is a mixture of propylene glycol methyl ether acetate and propylene glycol ethyl ether in a volume ratio of 1:1). Then, in the mixing vessel, the solvent is added first, followed by the polymer resin containing the protective group, the dissolution inhibitor, the photoacid generator, the acid quencher, and the surfactant. The mixture is stirred at room temperature for 4 hours to ensure complete dissolution. Then, it is circulated and filtered through a 0.1-micron nylon filter and a 5-nanometer polyethylene filter to obtain a uniform chemically amplified photoresist.

[0057] After preparing the chemically amplified photoresist, its performance was tested and found to be: particle count less than 0.1 particles / mL, metal ion content less than 1 ppb, moisture content less than 100 ppm, film thickness uniformity deviation less than ±1%, and photosensitivity of 30 mJ / cm². 2 The critical dimension uniformity is ±2 nanometers.

[0058] Example 3

[0059] This embodiment provides a method for using a platinum(II) complex-based chemical amplification photoresist, wherein the chemical amplification photoresist is the platinum(II) complex-based chemical amplification photoresist described in any of the above embodiments. The method of use includes:

[0060] A silicon wafer is provided, wherein the surface of the silicon wafer is provided with a thin film layer that is slightly alkaline or rich in dangling bonds;

[0061] The platinum(II) complex-based chemical amplification photoresist described in any of the above embodiments is coated on the silicon wafer, and the photolithographic pattern is obtained by pre-baking, exposure, post-baking and development.

[0062] Since the method of using the platinum(II) complex-based chemical amplification photoresist provided in this embodiment belongs to the same inventive concept as the platinum(II) complex-based chemical amplification photoresist provided in any of the above embodiments, the method of using the platinum(II) complex-based chemical amplification photoresist provided in this embodiment has at least all the advantages of the platinum(II) complex-based chemical amplification photoresist provided in the above embodiments. For the advantages of the method of using the platinum(II) complex-based chemical amplification photoresist provided in this embodiment, please refer to the relevant description of the beneficial effects of the platinum(II) complex-based chemical amplification photoresist provided in the above embodiments, which will not be repeated here.

[0063] To facilitate understanding of the present invention, the specific process of using the chemically amplified photoresist based on platinum(II) complexes provided in this embodiment is illustrated below by way of example.

[0064] First, a silicon wafer is provided with a slightly alkaline Si3N4 thin film layer on its surface, the film thickness of which is 100 nanometers. Then, a chemically amplified photoresist based on a platinum(II) complex, as described in any of the above embodiments, is spin-coated onto the silicon wafer under the following conditions: spin speed 1500 rpm, time 30 seconds. Next, it is placed on a hot plate and baked at 100 degrees Celsius for 90 seconds to obtain a photoresist film with a thickness of 0.3 micrometers. Then, exposure is performed using a KrF exposure machine (wavelength 248 nanometers) at an exposure dose of 30 mJ / cm². 2After exposure, bake at 110 degrees Celsius for 60 seconds. Finally, develop with a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds to obtain a clear photolithographic pattern.

[0065] In summary, the platinum(II) complex-based chemical amplification photoresist and its application provided by this invention have the following advantages: The platinum(II) complex-based chemical amplification photoresist provided by this invention comprises: a polymer resin containing a protecting group, a photoacid generator, an acid quencher, and a solvent; wherein the photoacid generator includes a first photoacid generator, which includes at least one platinum(II) complex. Therefore, the platinum(II) complex-based chemical amplification photoresist provided by this invention, by introducing a platinum(II) complex as the first photoacid generator, allows alkaline substances on the substrate surface to undergo ligand exchange with sulfonate ligands in the platinum(II) complex before exposure in a slightly alkaline or dangling bond-rich environment, forming a highly active hydroxyl intermediate; this intermediate efficiently dissociates under light irradiation, simultaneously releasing sulfonate anions and highly active hydroxyl radicals; these hydroxyl radicals initiate a chain reaction in the organic-rich photoresist environment, generating a large number of extra protons (H). + This results in a final effective acid quantity exceeding the initial number of coordinated sulfonate ligands, thus significantly increasing the photoacid generation efficiency after exposure compared to traditional photoacid generators. Furthermore, when the platinum(II) complex-based chemically amplified photoresist provided by this invention is used on a substrate with a slightly alkaline or dangling bond-rich thin film layer, it can generate sufficient effective acid. Even if some of the initial acid reacts with the substrate surface material, the protons (H+) generated in the chain reaction... + This method still ensures that the bottom of the photoresist exposure area fully completes the deprotection reaction, thereby effectively suppressing the formation of residues or traces and obtaining high-resolution photolithographic patterns with good morphology. Furthermore, using the platinum(II) complex-based chemically amplified photoresist provided by this invention eliminates the need for additional surface modification or anti-reflective coating processes, not only avoiding potential damage to the substrate but also simplifying the manufacturing process and reducing process complexity and cost.

[0066] Since the preparation method and usage method of the platinum(II) complex-based chemical amplification photoresist provided by this invention belong to the same inventive concept as the platinum(II) complex-based chemical amplification photoresist provided by this invention, they at least possess all the advantages of the platinum(II) complex-based chemical amplification photoresist provided by this invention. For details regarding the advantages of the preparation method and usage method of the platinum(II) complex-based chemical amplification photoresist provided by this invention, please refer to the relevant description of the beneficial effects of the platinum(II) complex-based chemical amplification photoresist provided by this invention; further details will not be repeated here.

[0067] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. A chemically amplified photoresist based on a platinum(II) complex, characterized in that, include: The invention comprises a polymer resin containing a protecting group, a photoacid generator, an acid quencher, and a solvent; wherein the photoacid generator includes a first photoacid generator, the first photoacid generator comprising at least one platinum(II) complex.

2. The chemically amplified photoresist based on platinum(II) complexes as described in claim 1, characterized in that, The chemically amplified photoresist further includes additives, which include at least one of a dissolution inhibitor, a surfactant, and a stabilizer. In the chemically amplified photoresist, by weight percentage, the polymer resin containing a protecting group is 1% to 20%, the photoacid generator is 0.2% to 5%, the first photoacid generator is 0.1% to 2%, the acid quencher is 0.1% to 2%, the solvent is 75% to 98%, and the dissolution inhibitor, the surfactant, and the stabilizer are all 0% to 0.3%.

3. The chemically amplified photoresist based on platinum(II) complexes as described in claim 1, characterized in that, The platinum(II) complexes include platinum(II)-bipyridine sulfonic acid complexes; The molecular formula of the platinum(II)-bipyridine sulfonic acid complex is: Where A is a molecular formula C a F 2a+1 Perfluoroalkyl, where a is an integer from 1 to 10; R is hydrogen or has the molecular formula C b H 2b+1 Alkyl groups, where b is an integer from 1 to 20.

4. The chemically amplified photoresist based on platinum(II) complexes as described in claim 1, characterized in that, The photoacid generator further includes a second photoacid generator, which includes at least one of thioonium salt photoacid generators, iodonium salt photoacid generators, and sulfonate photoacid generators.

5. The chemically amplified photoresist based on platinum(II) complexes as described in claim 1, characterized in that, The polymer resin containing the protecting group includes at least one of p-hydroxystyrene polymers containing the protecting group and acrylate polymers containing the protecting group.

6. The chemically amplified photoresist based on platinum(II) complexes as described in claim 1, characterized in that, The acid quencher includes basic amine compounds or weak acid onium salts.

7. The chemically amplified photoresist based on platinum(II) complexes as described in claim 1, characterized in that, The solvent includes at least one of propylene glycol methyl ether acetate, ethyl lactate, γ-butyrolactone, amyl acetate, methyl butyl acetate, propylene glycol methyl ether, propylene glycol ethyl ether, anisole, 2-heptanone, cyclohexanone, and cyclopentanone.

8. A method for preparing a chemically amplified photoresist based on a platinum(II) complex as described in any one of claims 1 to 7, characterized in that, The preparation method includes: The following components are weighed according to a preset ratio: a polymer resin containing a protecting group, a photoacid generator, an acid quencher, a dissolution inhibitor, a surfactant, and a solvent; wherein the photoacid generator includes a first photoacid generator, which includes at least one platinum(II) complex. The obtained solvent, the polymer resin containing the protective group, the dissolution inhibitor, the photoacid generator, the acid quencher, and the surfactant are sequentially added to a mixing container for mixing to obtain the chemically amplified photoresist.

9. The method for preparing a chemically amplified photoresist based on a platinum(II) complex as described in claim 8, characterized in that, The preset proportions include, by weight percentage, 1% to 20% of the polymer resin containing the protective group, 0.2% to 5% of the photoacid generator, 0.1% to 2% of the first photoacid generator, 0.1% to 2% of the acid quencher, 75% to 98% of the solvent, and 0% to 0.3% of both the dissolution inhibitor and the surfactant.

10. A method of using a chemically amplified photoresist based on a platinum(II) complex as described in any one of claims 1 to 7, characterized in that, The method of use includes: A silicon wafer is provided, wherein the surface of the silicon wafer is provided with a thin film layer that is slightly alkaline or rich in dangling bonds; The platinum(II) complex-based chemical amplification photoresist as described in any one of claims 1 to 7 is coated on the silicon wafer, and the photolithographic pattern is obtained by pre-baking, exposure, post-baking and development.

Images