Electrolyte composition and mask plate

Abstract

The application discloses an electrolyte composition and a mask plate. The electrolyte composition comprises a corrosion inhibitor, and the corrosion inhibitor comprises a first component and a second component. The first component contains a phosphoric acid group and an amine group. The phosphoric acid group has the function of integrating metal ions, can preferentially integrate metal ions in water, and helps the second component to act on the FMM surface to remove interference, thereby improving the cleaning efficiency of the first component on the FMM. The amine group can be adsorbed on the surface of the FMM to form a basic protective film through the lone pair of electrons of the nitrogen atom. At the same time, the second component contains a carbon-nitrogen double bond, the carbon-nitrogen double bond can have site interaction with the amine group in the first component and / or the surface of the FMM, and the two can be co-adsorbed at the interface, which helps to form a denser and more complete protective film, so that the corrosion inhibition and cleaning effect are significantly enhanced, and the electrolyte composition simultaneously has high cleaning efficiency and excellent corrosion inhibition performance.

Description

Technical Field

[0001] This application relates to the technical field of vapor deposition, and more particularly to an electrolyte composition and a mask. Background Technology

[0002] A fine metal mask (FMM) is an ultra-thin, high-precision metal sheet, typically made of nickel-iron alloy, with a thickness of only tens of micrometers and an extremely low coefficient of thermal expansion. In the vapor deposition process of displays such as OLEDs, FMMs are used to precisely position the vapor-deposited material to form pixel patterns, and the precision of these patterns directly affects the resolution and image quality of the display.

[0003] During the vapor deposition process, contaminants such as organic light-emitting materials, metal particles, and environmental dust can easily adhere to the surface of the FMM and its micron-sized slits. If cleaning is not thorough, the residues will clog the openings, leading to problems such as uneven vapor deposition, color deviation, and decreased brightness. In severe cases, it can even cause permanent damage to the FMM.

[0004] Currently, the industry commonly uses electrolytic cleaning to clean FMMs. This method places the FMM as the cathode in an electrolyte, where electrochemical polarization generates hydrogen bubbles on the cathode surface. These bubbles then physically remove contaminants. However, current electrolyte systems often struggle to balance high cleaning efficiency with long-term protection, and FMM corrosion can still occur under prolonged exposure or high current densities. Summary of the Invention

[0005] In view of this, this application provides an electrolyte composition and a mask, which aims to improve the problem that electrolytes are difficult to simultaneously achieve high cleaning efficiency and excellent corrosion inhibition performance.

[0006] In a first aspect, the embodiments of this application are implemented as follows: an electrolyte composition comprising an electrolyte, a corrosion inhibitor, an additive, and a solvent; The corrosion inhibitor comprises a first component and a second component, wherein the first component contains amine groups and phosphate groups, and the second component contains carbon-nitrogen double bonds.

[0007] Optionally, in some embodiments of this application, the first component has a structure as shown in formula (1): R-nN [CH2 PO(OX)2] m R is selected from hydrogen atoms or alkyl groups; m and n are each independently selected from any integer from 1 to 3; X can be one of sodium, potassium, calcium, or organic amines.

[0008] Optionally, in some embodiments of this application, the second component has a structure as shown in formula (2): R1–CH = N–R2 (2); R1 and R2 are each independently selected from at least one of hydrogen atom, substituted or unsubstituted alkyl group, and substituted or unsubstituted aryl group.

[0009] Optionally, in some embodiments of this application, the first component includes at least one of sodium aminoalkylphosphonate, potassium aminoalkylphosphonate, and calcium aminoalkylphosphonate; and / or The second component includes Schiff base compounds.

[0010] Optionally, in some embodiments of this application, the mass ratio of the first component to the second component ranges from 1 to 1.5.

[0011] Optionally, in some embodiments of this application, the electrolyte includes at least one of potassium hydroxide, lithium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, rubidium hydroxide, cesium hydroxide, francium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium borate, sodium metasilicate, and trisodium phosphate.

[0012] Optionally, in some embodiments of this application, the adjuvant includes at least one of a chelating agent, a dispersant, and a surfactant; The surfactant includes alkylphenol polyoxyethylene ether; The chelating agent includes at least one of citrate, tartrate, oxalate, malate, ethylenediaminetetraacetic acid and its salts, tricarboxylic acid aminotriacetic acid and its salts, and polyaspartic acid. The dispersant includes at least one of sodium polyacrylate, polymaleic anhydride, cocamidopropyl betaine, sodium dodecyl sulfate, and sodium polystyrene sulfonate.

[0013] Optionally, in some embodiments of this application, the electrolyte composition comprises the following components in parts by weight: The water-soluble electrolyte comprises 5 to 8 parts, the corrosion inhibitor comprises 0.02 to 0.5 parts, the additive comprises 0.01 to 1 part, and the solvent comprises 90 to 95 parts.

[0014] Secondly, embodiments of this application provide a mask obtained by cleaning with the electrolyte composition as described above.

[0015] Optionally, in some embodiments of this application, the material of the mask includes a nickel-iron alloy.

[0016] The electrolyte composition of this application embodiment includes a corrosion inhibitor, which comprises a first component and a second component. The first component contains phosphate and amine groups. The phosphate groups have the function of integrating metal ions, preferentially integrating metal ions in the water, which helps to remove interference from the second component acting on the FMM surface, thereby improving the cleaning efficiency of the first component on the FMM. The amine groups, through the lone pair electrons of the nitrogen atom, can adsorb onto the FMM surface to form a basic protective film. Simultaneously, the second component contains carbon-nitrogen double bonds, which can interact with the amine groups in the first component and / or the FMM surface at specific sites. Co-adsorption occurs at the interface, helping to form a denser and more complete protective film, significantly enhancing both corrosion inhibition and cleaning effects. Therefore, the electrolyte composition simultaneously possesses both high cleaning efficiency and excellent corrosion inhibition performance. Attached Figure Description

[0017] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 This is a schematic diagram of the planar structure of the mask in some embodiments of this application; Figure 2 These are microscope (a) and scanning electron microscope (b) photographs of the FMM before testing in Example 1 provided in this application; Figure 3 These are microscope photographs of Examples 1 and Comparative Examples 1-3 provided in this application after testing.

[0019] Explanation of reference numerals in the attached figures: 10. Substrate; 101. Mask hole. Detailed Implementation

[0020] 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. Furthermore, it should be understood that the specific embodiments described herein are only for illustration and explanation of this application and are not intended to limit this application. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains.

[0021] An ideal FMM electrolyte must meet several stringent requirements: First, it must have good conductivity to ensure cleaning efficiency; second, it needs to effectively remove various contaminants while providing excellent corrosion inhibition and protection for the nickel-iron alloy substrate to prevent surface corrosion or hydrogen embrittlement caused by the cleaning process itself; and third, the cleaning solution should have good stability and operational safety.

[0022] Currently, common alkaline or weakly acidic electrolyte systems often fail to achieve both efficient cleaning and long-term protection, especially lacking specialized corrosion inhibitors for special materials such as Invar alloys. Under prolonged or high-current-density operation, corrosion of the alloys may still occur.

[0023] Therefore, embodiments of this application provide an electrolyte composition and a mask, which aim to enable the electrolyte composition to simultaneously possess high cleaning efficiency and excellent corrosion inhibition properties.

[0024] According to a first aspect of the embodiments of this application, an electrolyte composition is provided, the electrolyte composition comprising a water-soluble electrolyte, a corrosion inhibitor, an additive, and a solvent; The corrosion inhibitor comprises a first component and a second component. The first component contains amine and phosphate groups, and the second component contains carbon-nitrogen double bonds.

[0025] By adopting the above scheme, the first component contains phosphate and amine groups. The phosphate groups can integrate metal ions, preferentially integrating them in the water, which helps to remove interference from the second component acting on the FMM surface, thereby improving the cleaning efficiency of the first component on the FMM. The amine groups, through the lone pair electrons of the nitrogen atom, can adsorb onto the FMM surface to form a basic protective film. At the same time, because the second component contains carbon-nitrogen double bonds, these bonds can interact with the amine groups in the first component and / or the FMM surface, resulting in co-adsorption at the interface. This helps to form a denser and more complete protective film, significantly enhancing the corrosion inhibition and cleaning effects. Thus, the electrolyte composition simultaneously possesses both high cleaning efficiency and excellent corrosion inhibition performance. In summary, the first component focuses on ion integration and primary adsorption, while the second component focuses on surface film formation and corrosion inhibition. The two components complement each other in space and function, achieving "three-dimensional protection" against surface contamination and substrate corrosion.

[0026] In some embodiments, the first component has a structure as shown in formula (1): R-nN [CH2 PO(OX)2] m R is selected from hydrogen atoms or alkyl groups; m and n are each independently selected from any integer from 1 to 3; X can be one of sodium, potassium, calcium, or organic amines.

[0027] By employing the above scheme, the first component contains phosphate groups, which can act as strong adsorption groups to effectively adsorb substances. The first component also contains amine groups, which can act as multi-site coordination centers, coordinating with empty orbitals on the FMM surface through the lone pair electrons of the nitrogen atom to form chelate or bridged adsorption, thus forming a basic protective film on the FMM surface. Simultaneously, the first component also contains alkyl chains, which help to block the penetration of water molecules and ions, thereby forming a more ordered and compact molecular self-assembled layer. Furthermore, the methylene group separates the phosphate groups from the main chain, preventing the amine groups from adversely interfering with the electronic effects of the phosphate groups, allowing the phosphate groups to maintain independent strong coordination and adsorption capacity. The terminal group R can effectively integrate metal ions in the water, preventing metal ions from depositing on the FMM surface during cleaning and forming scale, thereby maintaining the cleanliness of the solid-liquid interface on the FMM surface.

[0028] In some embodiments, the second component has a structure as shown in formula (2): R1–CH = N–R2 (2); R1 and R2 are each independently selected from at least one of hydrogen atom, substituted or unsubstituted alkyl group, and substituted or unsubstituted aryl group.

[0029] By adopting the above scheme, the nitrogen atom in the carbon-nitrogen double bond has a lone pair of electrons, which can act as an electron donor and be strongly adsorbed on the anodic active region with low electron density on the FMM surface. This adsorption is achieved through a combination of coordination bonds and physical adsorption. At the same time, by flexibly selecting R1 and R2, the hydrophobicity, steric hindrance and electron cloud density of the molecule can be precisely controlled.

[0030] In some embodiments, the first component includes at least one of sodium aminoalkylphosphonate, potassium aminoalkylphosphonate, and calcium aminoalkylphosphonate. Aminoalkylphosphonates are nitrogen-containing polyphosphonic acids that possess both corrosion inhibition and chelating functions. The phosphate groups in their molecular structure have a strong chelating ability for metal ions such as calcium, magnesium, iron, and nickel in water. This not only prevents metal ions from depositing on the mask surface to form a scale layer, but also effectively chelates the stripped metal oxide dirt, dispersing it in the solution and preventing secondary pollution, thereby improving cleaning efficiency. Through the phosphonic acid and amino groups in the molecule, it can stably chemically adsorb onto the FMM surface, forming a dense protective film. This film can effectively block corrosive ions in the electrolyte (such as OH-). - These compounds significantly inhibit the anodic dissolution reaction of metals during electrolysis, providing long-term protection for the alloy matrix. They also exhibit excellent chemical stability, particularly in high-temperature, high-alkalinity, or high-salinity electrolyte systems, ensuring durable and reliable corrosion inhibition performance during long-term electrolytic cleaning.

[0031] In some embodiments, the second component comprises a Schiff base compound. Schiff bases are a class of organic compounds containing an imine group (C=N-), whose unique molecular structure endows them with excellent corrosion inhibition properties. The nitrogen atom in the imine group (C=N-) contains a lone pair of electrons, which can form stable coordination bonds with empty d orbitals on the surface of nickel-iron alloys, thereby firmly adsorbing onto the active sites on the metal surface. This adsorption is very strong, forming a tight monolayer or multilayer protective film on the metal surface. Schiff bases are typically hybrid corrosion inhibitors, simultaneously inhibiting the cathodic hydrogen evolution reaction and the anodic metal dissolution reaction during electrolysis, thus comprehensively reducing the corrosion rate of the metal. By selecting different aldehyde and amine reactants, the molecular structure of the Schiff base can be flexibly controlled, thereby introducing different hydrophobic or hydrophilic groups. This flexibility in molecular design allows for precise optimization of the adsorption capacity of the corrosion inhibitor on specific metal surfaces and the hydrophobic shielding performance of the formed protective film, according to specific needs.

[0032] In some embodiments, the mass ratio of the first component to the second component ranges from 1 to 1.5. For example, the mass ratio of the first component to the second component can be 1, 1.1, 1.2, 1.3, 1.4, 1.5, or any value between two adjacent values ​​mentioned above.

[0033] By employing the above scheme, the aminoalkyl phosphate groups in the first component preferentially occupy the main active sites on the FMM surface through strong chemisorption, forming a basic protective film. Simultaneously, the second component, through physicochemical adsorption and intermolecular interactions with the first component, fills the gaps between the molecules of the first component and covers the remaining weak adsorption sites. With the mass ratio of the first to second components within a suitable range, the interfacial assembly behavior of the two functional molecules is precisely controlled at the molecular level, achieving the optimal match between "chemical anchoring" and "hydrophobic shielding" functions and maximizing "intermolecular cross-linking," thereby constructing a dense, stable, and synergistically effective composite corrosion-inhibiting protective film. If the mass ratio of the first to second components is less than 1, gaps will appear between the "anchor points" formed by the first component, preventing the second component from completely covering and "locking" them, resulting in defects in the protective film and easy penetration by corrosive media. If the mass ratio of the first to second components is greater than 1.5, excess second component may not be fully and effectively adsorbed on the FMM surface, with some remaining free in the solution, potentially affecting the effective anchoring of the first component.

[0034] In some embodiments, the electrolyte includes at least one of potassium hydroxide, lithium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, rubidium hydroxide, cesium hydroxide, francium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium borate, sodium metasilicate, and trisodium phosphate.

[0035] In some embodiments, the adjuvant includes at least one of a chelating agent, a dispersant, and a surfactant. Different types of adjuvants are selected to suit different application requirements.

[0036] In some embodiments, the surfactant includes alkylphenol polyoxyethylene ether.

[0037] By employing the above-mentioned scheme, one end of the alkylphenol polyoxyethylene ether is a hydrophobic alkylphenol (lipophilic), and the other end is a polyoxyethylene chain (hydrophilic). This structure significantly reduces the surface tension of the electrolyte composition, allowing it to spread onto the FMM surface instantly upon contact, thus ensuring thorough cleaning. Simultaneously, the alkylphenol polyoxyethylene ether can penetrate the tiny gaps between contaminants and the FMM surface, weakening the adhesion strength of the contaminants. When hydrogen microbubbles generated during electrolysis peel oil or organic residues from the surface, the alkylphenol polyoxyethylene ether can quickly encapsulate these hydrophobic contaminant particles or droplets, suspending and dispersing them stably in the electrolyte through steric hindrance, forming emulsions or micelles. This emulsifies and disperses the contaminants, preventing secondary deposition. Furthermore, the ether bond (-O-) in the alkylphenol polyoxyethylene ether is very stable under alkaline conditions, meeting the high alkalinity requirements of the electrolyte composition and reducing performance degradation.

[0038] In some embodiments, the chelating agent includes at least one of citrate, tartrate, oxalate, malate, ethylenediaminetetraacetic acid and its salts, tricarboxylic acid aminotriacetic acid and its salts, and polyaspartic acid.

[0039] By employing the above methods, these chelating agents can efficiently chelate impurities in the dirt on the FMM surface, accelerate the cleaning process, and reduce potential damage to the FMM surface.

[0040] In some embodiments, the dispersant includes at least one of sodium polyacrylate, polymaleic anhydride, cocamidopropyl betaine, sodium lauryl sulfate, and sodium polystyrene sulfonate.

[0041] In some embodiments, the electrolyte composition comprises the following components in parts by weight: Five to eight parts of electrolyte, 0.02 to 0.5 parts of corrosion inhibitor, 0.01 to 1 part of additive, and 90 to 95 parts of solvent.

[0042] In some embodiments of this application, the solvent may include a combination of water and organic solvents.

[0043] In some embodiments of this application, the resistivity of water in the solvent is greater than 18 MΩ / cm. Water with a high resistivity can serve as a favorable solvent in the electrolyte, allowing it to fully ionize and providing the necessary ionic conductivity for the electrolytic cleaning process.

[0044] In some embodiments of this application, the organic solvent may include at least one of ethanol, ethylene glycol, propylene glycol, glycerol, isopropanol, isoamyl alcohol, n-butanol, cyclohexanol ethylene glycol butyl ether, and diethylene glycol monomethyl ether.

[0045] By employing the above method, contaminants on the FMM surface also include residual organic light-emitting materials from vapor deposition. These contaminants can be dissolved in organic solvents, which helps improve the electrolyte's solubility in these types of contaminants. If water is used alone as a solvent, its high surface tension prevents effective wetting and penetration into the microstructure of the FMM surface. Organic solvents, on the other hand, reduce surface tension, facilitating rapid spread of the electrolyte and penetration into micron-level crevices, ensuring strong cleaning power and corrosion inhibition.

[0046] According to a second aspect of the embodiments of this application, a mask is provided, which is obtained by cleaning with the electrolyte composition as described above.

[0047] Please see Figure 1 The photomask includes a substrate 10 with mask holes 101, through which vapor deposition material can pass and be deposited in the photomask. The photomask in this embodiment has a clean surface and excellent corrosion inhibition capability.

[0048] In some embodiments, the mask material includes a nickel-iron alloy.

[0049] By adopting the above scheme, nickel-iron alloy (Invar alloy), due to its extremely low coefficient of thermal expansion, is the only mainstream material for manufacturing high-precision FMMs and is widely used in the fine metal mask evaporation process of OLED display panels. Nickel-iron alloy forms a mixed oxide layer mainly composed of Fe2O3, Fe3O4, and NiO in air. The molecular design of the corrosion inhibitor (first component and second component) of this invention is optimized specifically for the chemical properties of the iron and nickel oxide surfaces. For example, phosphate groups have a specific high affinity for iron oxides, and amine groups have a specific high affinity for nickel sites. Nickel-iron alloy contains both iron and nickel, and their electrochemical behaviors differ. The compounded corrosion inhibitor may achieve synergistic protection of the bimetallic system and prevent galvanic corrosion through selective adsorption or the formation of a co-adsorption film on different metal phases.

[0050] The present application will be specifically described below through specific embodiments. These embodiments are only some embodiments of the present application and are not intended to limit the present application. Unless otherwise specified, the raw materials used in the following embodiments are all commercially available products.

[0051] Example 1 An electrolyte composition is prepared by the following method: Prepare 5.0% potassium hydroxide (KOH), 0.05% hydroxyethylidene diphosphonic acid (HEDP), 0.05% salicylaldehyde ethylenediamine Schiff base, 0.025% alkylphenol polyoxyethylene ether (OP-10), 0.025% disodium ethylenediaminetetraacetate (EDTA-2Na), 0.05% sodium molybdate, 1.5% ethanol, and 93.3% deionized water; Deionized water was added to a stirring container, and KOH was added sequentially at room temperature and stirred until completely dissolved. Then, HEDP, EDTA-2Na, OP-10, sodium molybdate and ethanol were slowly added, and the mixture was stirred continuously for at least 60 minutes until the solution was homogeneous and transparent to obtain the electrolyte composition. The mass ratio of the first component (HEDP) to the second component (salicylaldehyde ethylenediamine Schiff base) was 1.0.

[0052] Example 2 The difference from Example 1 lies in the change of the type of the second component. In this example, o-vanillin acetalized o-phenylenediamine Schiff base is used instead of salicylaldehyde acetalized ethylenediamine Schiff base, and its addition amount is maintained at 0.05%. The types, contents and preparation methods of the other components are the same as in Example 1.

[0053] Example 3 The difference from Example 1 lies in the change of the type of the second component. In this example, 2-pyridinecarboxaldehyde thiourea Schiff base is used instead of salicylaldehyde ethylenediamine Schiff base, and its addition amount is maintained at 0.05%. The types, contents and preparation methods of the other components are the same as in Example 1.

[0054] Example 4 The difference from Example 1 lies in the change of the type of the first component. In this example, the second component is still 0.05% salicylaldehyde ethylenediamine Schiff base. The first component is replaced by sodium aminotrimethylphosphonate (ATMP·Na5) as the second component, and its addition amount is 0.05%. The types, contents and preparation methods of the remaining components are the same as in Example 1.

[0055] Example 5 The difference from Example 1 lies in changing the mass ratio of the first component to the second component. In this example, the amount of the first component (HEDP) added is 0.05%, the amount of the second component (salicylaldehyde ethylenediamine Schiff base) added is 0.075%, and the mass ratio of the first component to the second component is 1.5; the types, contents, and preparation methods of the remaining components are the same as in Example 1.

[0056] Example 6 The difference from Example 1 lies in changing the mass ratio of the first component to the second component. In this example, the amount of the first component (HEDP) added is 0.05%, the amount of the second component (salicylaldehyde ethylenediamine Schiff base) added is 0.04%, and the mass ratio of the first component to the second component is 0.8; the types, contents, and preparation methods of the remaining components are the same as in Example 1.

[0057] Example 7 The difference from Example 1 lies in changing the mass ratio of the first component to the second component. In this example, the amount of the first component (HEDP) added is 0.05%, the amount of the second component (salicylaldehyde ethylenediamine Schiff base) added is 0.09%, and the mass ratio of the first component to the second component is 1.8; the types, contents, and preparation methods of the remaining components are the same as in Example 1.

[0058] Comparative Example 1 An electrolyte composition differs from Example 1 in that it does not contain a second component (Schiff base) and only contains the first component (HEDP, 0.05%). The composition is: KOH (5%), HEDP (0.05%), OP-10 (0.025%), EDTA-2Na (0.025%), sodium molybdate (0.05%), ethanol (1.5%), and deionized water (93.35%). The preparation method is the same as in Example 1.

[0059] Comparative Example 2 An electrolyte composition differs from Example 1 in that it omits the first component (sodium alkylaminophosphonate) and contains only the second component (salicylaldehyde ethylenediamine Schiff base, 0.05%). The composition is: KOH (5%), salicylaldehyde ethylenediamine Schiff base (0.05%), OP-10 (0.025%), EDTA-2Na (0.025%), sodium molybdate (0.05%), ethanol (1.5%), and deionized water (93.35%). The preparation method is the same as in Example 1.

[0060] Comparative Example 3 An electrolyte composition differs from that of Example 1 in that it omits both the first component (sodium alkylaminophosphonate) and the second component (Schiff base). The composition is: KOH (5%), OP-10 (0.025%), EDTA-2Na (0.025%), sodium molybdate (0.05%), ethanol (1.5%), and deionized water (93.40%). The preparation method is the same as in Example 1.

[0061] Performance testing: The following test methods were used to assess the electrolytic cleaning effect of the electrolyte compositions of Examples 1-7 and Comparative Examples 1-3 on photomasks: 1. Cut the FMM to a size of 2.0 cm × 3.0 cm and connect it to the cathode electrode. Use the platinum titanium mesh electrode as the anode for electrolysis. 2. Prepare the electrolytes for the examples and comparative examples; 3. Place the electrodes in the electrolyte at 25°C. o Cleaning was performed by electrolysis at room temperature (C) for 10 minutes, followed by a long-term corrosion test of 300 hours. After electrolysis for the specified time, the electrolyte residue on the electrodes was rinsed with isopropanol and then cleaned with pure water. The electrodes were then dried with nitrogen gas and observed under an optical microscope (OM). a. Bubble performance: Air is bubbled into a graduated cylinder for an extended period, and the real-time height of the foam layer over time is recorded. After stabilization, it is observed whether the bubble height increases over time. b. Cleaning effect: An organic light-emitting material is deposited on the mask by evaporation, followed by electrolytic cleaning. OM (50x) is used to check whether there is any organic material residue on the mask surface after cleaning. c. 100h constant current corrosion: Using a potentiostat, at 30 mA·cm⁻¹ -2 A 100-hour long-term corrosion experiment was conducted at a specific current density: a constant current mode was set on the potentiostat, and the current density was set to 30 mA·cm². -2 The total experimental time was set to 100 hours. After the experiment, polarization was stopped first, and then the working electrode was taken out to observe the electrode surface and compare it with the state before the experiment. d. Anodic corrosion: Platinum plating (Pt-Ti) is used as the anode on the titanium surface. The presence of corrosion on the Pt-Ti surface is observed, and the degree of blackening is used to determine whether corrosion has occurred. After the 300h test is completed, the electrolyte is sent for ICP-MS testing. The metal ion concentrations before and after the test are compared to see if they have increased (whether the iron and nickel ions in the mask have been dissolved into the electrolyte; extremely low: ion increase in electrolyte ≤3%, low: 3% ≤ ion increase in electrolyte ≤5%, low: 5% ≤ ion increase in electrolyte ≤10%, moderate: 10% ≤ ion increase in electrolyte ≤20%, significant increase: ion increase in electrolyte >20%). The weight change of the mask before and after the test is also compared and the amount of weight change is recorded.

[0062] The test results are shown in Table 1.

[0063] Comparing Examples 1-7 with Comparative Examples 1-3, Examples 1-7 used a combination of the first and second components, while Comparative Example 1 used only the first component, Comparative Example 2 used only the second component, and Comparative Example 3 lacked both the first and second components. As shown in Table 1, the cleaning effect of Examples 1-7 was superior to that of Comparative Examples 1-3. This indicates a positive synergy between the dispersion and chelation capabilities of phosphonates and the strong adsorption and penetration capabilities of Schiff bases, resulting in more effective removal of organic matter and prevention of redeposition. Furthermore, considering the 300-hour weight change, ICP data, and 100-hour corrosion inhibition rate, the protective effect of Examples 1-7 was significantly higher than that of Comparative Examples 1-3. This suggests that Schiff base and phosphonates formed a dense composite protective film on the metal surface, with complementary corrosion inhibition mechanisms. In addition, the anodes of Examples 1-7 remained intact, demonstrating that the composite film also provided excellent protection for the anodic region. In contrast, the anodes of Comparative Examples 1-3 were severely blackened, indicating that single-component solutions or blank solutions could not protect the anode under strong oxidation potentials. In addition, since the increase in Fe / Ni ion concentration is highly positively correlated with the mask weight loss and the degree of surface yellowing, Example 1 showed the least dissolution, indicating that the protective film formed was the densest.

[0064] like Figure 2 As shown, the FMM before testing exhibited a smooth surface and showed no signs of corrosion such as yellowing in microscopic and scanning electron microscope images. After 100 hours and a current density of 30 mA·cm⁻¹, -2 After long-term corrosion experiments, the FMM surface showed obvious yellowing, as shown in the results. Figure 3 As shown in the figure. Comparison of corrosion under different electrolyte conditions revealed that the electrolyte composition in Example 1, using a combination of sodium aminoalkylphosphonate and Schiff base as a corrosion inhibitor, exhibited the least corrosion; the electrolyte without an inhibitor (Comparative Example 3) showed the most severe corrosion; and the electrolyte with only the second component showed the next least corrosion. Therefore, sodium aminoalkylphosphonate, as a corrosion inhibitor, has a significant protective effect on FMM in the electrolyte. Furthermore, the corrosion inhibition effect of using sodium aminoalkylphosphonate in combination with Schiff base is better than using either sodium aminoalkylphosphonate or Schiff base alone, indicating a synergistic effect between the two.

[0065] Compared with Examples 1, Examples 5-7 and Table 1, the optimal ratio of the first component to the second component is 1:1-1.5:1. An excessive amount of the first component will lead to too many bubbles, which may form an excessively thick adsorption film and affect cleaning; while a relatively insufficient amount of the first component will lead to insufficient dispersion and chelation ability, resulting in a decrease in cleaning and corrosion inhibition effects.

[0066] Based on Examples 1-4 and Table 1, it can be seen that Example 1 (Salicylaldehyde ethylenediamine) > Example 3 (Pyridine) > Example 2 (o-vanillin). The rigidity of the salicylaldehyde structure and the strong coordination of the phenolic hydroxyl group make its adsorption and synergistic effect the best. Example 1 (HEDP) > Example 4 (ATMP). In a strong alkaline oxidizing environment, HEDP (CP bond) may be more stable than ATMP (NP bond), and its molecular structure has a higher degree of synergistic spatial matching with the Schiff base used.

[0067] The electrolyte composition and mask provided in the embodiments of this application have been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of this application. The description of the above embodiments is only for the purpose of helping to understand the method and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. An electrolyte composition, characterized in that, The electrolyte composition includes an electrolyte, a corrosion inhibitor, an additive, and a solvent; The corrosion inhibitor comprises a first component and a second component, wherein the first component contains amine groups and phosphate groups, and the second component contains carbon-nitrogen double bonds.

2. The electrolyte composition according to claim 1, characterized in that, The first component has the structure shown in formula (1): R-nN [CH2 PO(OX)2] m R is selected from hydrogen atoms or alkyl groups; m and n are each independently selected from any integer from 1 to 3; X can be one of sodium, potassium, calcium, or organic amines.

3. The electrolyte composition according to claim 1, characterized in that, The second component has the structure shown in formula (2): R1–CH = N–R2 (2); R1 and R2 are each independently selected from at least one of hydrogen atom, substituted or unsubstituted alkyl group, and substituted or unsubstituted aryl group.

4. The electrolyte composition according to any one of claims 1 to 3, characterized in that, The first component comprises at least one of sodium aminoalkylphosphonate, potassium aminoalkylphosphonate, and calcium aminoalkylphosphonate; and / or The second component includes Schiff base compounds.

5. The electrolyte composition according to claim 1, characterized in that, The mass ratio of the first component to the second component ranges from 1 to 1.

5.

6. The electrolyte composition according to any one of claims 1 to 5, characterized in that, The electrolyte includes at least one of potassium hydroxide, lithium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, rubidium hydroxide, cesium hydroxide, francium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium borate, sodium metasilicate, and trisodium phosphate.

7. The electrolyte composition according to any one of claims 1 to 5, characterized in that, The auxiliary agent includes at least one of chelating agents, dispersants, and surfactants; The surfactant includes alkylphenol polyoxyethylene ether; The chelating agent includes at least one of citrate, tartrate, oxalate, malate, ethylenediaminetetraacetic acid and its salts, tricarboxylic acid aminotriacetic acid and its salts, and polyaspartic acid. The dispersant includes at least one of sodium polyacrylate, polymaleic anhydride, cocamidopropyl betaine, sodium dodecyl sulfate, and sodium polystyrene sulfonate.

8. The electrolyte composition according to any one of claims 1 to 5, characterized in that, The electrolyte composition comprises the following components in parts by weight: The electrolyte comprises 5 to 8 parts, the corrosion inhibitor comprises 0.02 to 0.5 parts, the additive comprises 0.01 to 1 part, and the solvent comprises 90 to 95 parts.

9. A photomask, characterized in that, It is obtained by cleaning with the electrolyte composition as described in any one of claims 1 to 8.

10. The photomask according to claim 9, characterized in that, The material of the mask includes a nickel-iron alloy.

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