Corrosion-resistant cleaning composition, preparation method thereof and electronic device cleaning method
By adding metal salt compounds and chelating agents to the cleaning agent, the problem of removing halogen residues from electronic devices is solved, and the corrosion resistance of the cleaning agent and the weather resistance of the devices are improved.
Patent Information
- Application Number
- CN202511269247.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-05
- Publication Date
- 2025-12-12
AI Technical Summary
Existing cleaning agents are ineffective at removing halogen-containing residues, especially organic fluorine compounds, from electronic devices, leading to corrosion threats and low electrical performance.
A cleaning composition comprising metal salt compounds, chelating agents, synergists, and organic solvents is used to chemically disrupt the structure of residues and selectively capture halide ions to form stable complexes, preventing their redeposition and enhancing cleaning ability.
It significantly improves the removal capacity of halogen residues, reduces corrosion of the substrate medium, improves the weather resistance and electrical yield of the device, enhances the weather resistance of the device, reduces halogen corrosion of the substrate, improves the weather resistance of the device, and enhances the corrosion resistance of the cleaning agent.
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Figure CN121109072A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of electronic device cleaning, in particular to an anti-corrosion cleaning composition and a preparation method thereof, and especially to a high anti-corrosion composition for removing residues such as polymers, organic metal compounds and inorganic particles in electronic devices and applications. BACKGROUND
[0002] Chemical cleaning agents are important processes throughout the production and manufacturing of electronic devices, aiming to remove various residues including organic matter, organic metal compounds, inorganic oxides and particles generated in each process of production and manufacturing, so as to avoid adverse effects on production processes and product reliability. With the development of electronic science and technology, electronic devices are developing towards miniaturization and greater connection density, and therefore higher requirements are put forward for chemical cleaning agents. Not only do they need strong cleaning ability to remove all residues, but also they need to avoid attacking or damaging the substrate medium.
[0003] The production and manufacturing of electronic devices need to go through various complex and numerous processes, and are affected by manufacturing materials and environment. Halogen-containing compounds, including organic halogen-containing small molecules and polymers, halogen ions, etc., are inevitably introduced into the residues to be removed in some processes. These halogen-containing residues are extremely difficult to remove, especially for fluorine-containing residues. Organic fluorine compounds are stable in structure, and some organic metal fluorides formed under certain conditions are more stubborn. The presence of fluoride ions also poses a threat to the corrosion of the substrate medium, and the residual fluoride ions after cleaning can cause low electrical performance yield and poor weather resistance of electronic device products.
[0004] Cleaning agents for electronic devices are usually formula-type chemicals, and their main components include solvents or water, etchants and various functional additives. The residues on electronic devices are complex, and the substrate media to be protected are diverse, often requiring special combinations of functional additives to achieve a balance between high cleaning performance and high corrosion resistance. SUMMARY
[0005] In order to overcome the defects of the prior art, in response to market demand, the present application provides a high anti-corrosion cleaning composition which, while removing various residues, has high anti-corrosion properties for metal / non-metal medium materials to be protected in various processes of electronic device production and manufacturing.
[0006] The first aspect of the present application provides an anti-corrosion cleaning composition, which can include: 0.01 wt% to 10 wt% of a metal salt compound, 0.1 wt% to 10 wt% of a chelating agent, 1 wt% to 50 wt% of a synergist, and The remaining organic solvent, based on the total weight of the cleaning composition, The synergist may include amine compounds and water; The metal salt compound may be selected from one or more of sodium acetate, potassium acetate, lithium carbonate, and aluminum sulfate; The chelating agent may be a compound containing coordinating atoms, which may be selected from one or more of oxygen atoms, nitrogen units, sulfur atoms, and phosphorus atoms.
[0007] According to the cleaning composition of the first aspect, the cleaning composition may include 1 wt% to 10 wt%, preferably 1 wt% to 5 wt% water, based on the total weight of the cleaning composition.
[0008] According to the cleaning composition of the first aspect, the amine compound may be selected from one or more of primary amines, secondary amines, tertiary amines, and organic ammonium salts; Preferably, the amine organic compound may be selected from one or more of triethanolamine, diethanolamine, tetramethylammonium hydroxide, ethanolamine, and diethylamine.
[0009] According to the cleaning composition of the first aspect, the chelating agent may be selected from one or more of catechol, phthalic acid, and ethylenediaminetetraacetic acid.
[0010] According to the cleaning composition of the first aspect, the organic solvent may be a water-soluble organic solvent; Preferably, the organic solvent can be selected from... N -Methylpyrrolidone, N -Ethylpyrrolidone, dimethyl sulfoxide, sulfolane N , N -Dimethylformamide, N , N -One or more of the following: dimethylacetamide, diethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol, glycerol, n-butanol, cyclohexanol, and propylene glycol monomethyl ether acetate; More preferably, the water-soluble organic solvent may be selected from... N methylpyrrolidone, dimethyl sulfoxide, N , N -Dimethylformamide, diethylene glycol monomethyl ether N , N One or more of dimethylacetamide.
[0011] According to the cleaning composition of the first aspect, the cleaning composition may further include corrosion inhibitors, reducing agents and / or surfactants; Preferably, based on the total weight of the cleaning composition, the cleaning composition may include 0.1 wt% to 10 wt% of a corrosion inhibitor; 0.1 wt% to 10 wt% reducing agent; and / or Surfactants ranging from 0.1 wt% to 10 wt%.
[0012] According to the cleaning composition of the first aspect, the corrosion inhibitor may be a compound containing heteroatoms, wherein the heteroatoms are selected from one or more of oxygen atoms, nitrogen units, sulfur atoms, and phosphorus atoms; Preferably, the corrosion inhibitor may be selected from one or more of benzotriazole, sorbitol, and L-cysteine.
[0013] According to the cleaning composition of the first aspect, the reducing agent may be selected from one or more of thiourea dioxide, oxalic acid, and ascorbic acid.
[0014] The second aspect of this application provides a method for preparing the anti-corrosion cleaning composition of the first aspect, characterized in that the method may include: A metal salt compound, a chelating agent, and optionally a corrosion inhibitor, a reducing agent, and a surfactant are dissolved in an organic solvent to form a mixture. A synergist is then added to the mixture to obtain the corrosion-resistant cleaning composition.
[0015] A third aspect of this application provides a method for cleaning electronic devices, which may include: Electronic devices are cleaned using the corrosion-resistant cleaning composition of the first aspect or the corrosion-resistant cleaning composition prepared according to the preparation method of the second aspect. Preferably, the electronic device may include one or more of the following materials: silicon, sapphire, silicon carbide, aluminum, copper, gold, silver, nickel, titanium, tungsten, stainless steel, silicon dioxide, silicon nitride, gallium nitride, titanium nitride, aluminum nitride, high-k dielectric layer, and low-k dielectric layer.
[0016] The corrosion-resistant cleaning composition of this application may have, but is not limited to, the following beneficial effects: 1. It improves the ability of the cleaning composition to capture halogens and their ions, greatly enhances the resistance to corrosion by halogens and their ions, and improves the weather resistance of the device. 2. Improved the cleaning composition's ability to remove halogen-containing residues; 3. It expands the application range of the cleaning composition, which can be used to clean residues after various processes in the production and manufacturing of electronic devices. Attached Figure Description
[0017] Figure 1 A microscope image of the substrate to be cleaned after a dry etching process is shown.
[0018] Figure 2 A microscopic image of the test substrate after cleaning with the formulation of Example 4 is shown.
[0019] Figure 3 A microscopic image of the test substrate after cleaning with the formulation of Comparative Example 1 is shown. Detailed Implementation
[0020] The present application will be further described in detail below through embodiments. Through these descriptions, the features and advantages of the present application will become clearer and more apparent.
[0021] The term “exemplary” as used herein means “serving as an example, embodiment, or illustration.” Any embodiment illustrated herein as “exemplary” is not necessarily to be construed as superior to or better than other embodiments.
[0022] Furthermore, the technical features involved in the different embodiments of this application described below can be combined with each other as long as they do not conflict with each other.
[0023] The purpose of this application is to develop a highly corrosion-resistant cleaning composition that selectively captures halogens and their ions by adding metal salts, thereby greatly enhancing the cleaning composition's resistance to halogen and their ion corrosion, improving the weather resistance of devices, and increasing the cleaning composition's ability to remove halogen-containing residues.
[0024] This application provides a corrosion-resistant cleaning composition, which may include: 0.01 wt%~10 wt% metal salt compounds, 0.1 wt%~10 wt% chelating agent 1 wt%~50 wt% synergist, and The remaining organic solvent, based on the total weight of the cleaning composition, The synergist may include amine compounds and water; The metal salt compound may be selected from one or more of sodium acetate, potassium acetate, lithium carbonate, and aluminum sulfate; The chelating agent may be a compound containing coordinating atoms, wherein the coordinating atoms are selected from one or more of oxygen atoms, nitrogen units, sulfur atoms, and phosphorus atoms.
[0025] This application relates to a method for preparing a highly corrosion-resistant cleaning composition, and further to its application in the removal of halogen-containing residues in the field of electronic device manufacturing. The cleaning composition of this application significantly enhances the resistance to corrosion by selectively capturing halogens and their ions. The chelating agent can form stable complexes with metal ions, thereby preventing them from redepositing or re-adhering to the cleaned surface, thus improving the removal capacity of halogen-containing residues.
[0026] The cleaning principle of the cleaning composition of this application is as follows: During the manufacturing process of electronic devices, halogen-containing residues may be introduced due to the influence of manufacturing materials or the production environment. These residues are difficult to clean chemically, and the presence of halogen ions increases the risk of corrosion of electronic devices. Integrated circuit chip manufacturing has high technical requirements for chemical cleaning. Taking this as an example: after certain plasma dry etching processes, the residues on the wafer surface include halogen organic residues and inorganic residues. Halogen elements exist on the device surface of the wafer in both non-ionic and ionic forms. The cleaning composition of this application is a moderately strong alkaline solution. The alkaline compound destroys the structure of the residues through a chemical reaction, dissolving them in the cleaning agent for removal. Furthermore, under alkaline conditions, various materials on the device surface acquire a negative charge, greatly increasing the contact probability between the metal ions in the cleaning composition and the residues on the device surface. On the other hand, due to the strong binding ability of the metal positive ions in the cleaning composition to ionic halogens, the corrosion of the medium by halogen ions is effectively avoided while removing residues. Moreover, the excess metal positive ions will continue to attack non-ionic halogen residues and capture halogen elements, thus disintegrating the residues. Meanwhile, other components in the cleaning composition of this application will further strip and dissolve other broken-down residues, ultimately achieving complete removal of halogen residues, reducing halogen corrosivity, and enhancing the cleaning ability of the composition.
[0027] The cleaning composition of this application is used for cleaning electronic devices, and its application scope includes cleaning related to semiconductor and LED chip manufacturing, circuit boards, electronic packaging, and display panel manufacturing. The dielectric materials it protects include metallic materials such as aluminum, copper, gold, silver, nickel, titanium, and tungsten, as well as non-metallic materials such as silicon dioxide, silicon nitride, gallium nitride, high-k, and low-k materials. The cleaning targets include organic residues, inorganic residues, metal reaction byproducts, and particles.
[0028] In some embodiments, the cleaning composition may include 1 wt% to 50 wt% of an synergist, for example, the synergist content may be 1 wt%, 5 wt%, 10 wt%, 20 wt%, 25 wt%, 30 wt%, 40 wt%, 45 wt%, 50 wt%, or any combination of these values, based on the total weight of the cleaning composition.
[0029] In one embodiment, the cleaning composition may include 1 wt% to 10 wt%, preferably 1 wt% to 5 wt% water, based on the total weight of the cleaning composition.
[0030] In one embodiment, the amine compound may be selected from one or more of primary amines, secondary amines, tertiary amines, and organic ammonium salts; Preferably, the amine organic compound is selected from one or more of triethanolamine, diethanolamine, tetramethylammonium hydroxide, ethanolamine, and diethylamine.
[0031] In one embodiment, the chelating agent may be selected from one or more of catechol, phthalic acid, and ethylenediaminetetraacetic acid.
[0032] In one embodiment, the organic solvent may be a water-soluble organic solvent; Preferably, the organic solvent can be selected from... N -Methylpyrrolidone, N -Ethylpyrrolidone, dimethyl sulfoxide, sulfolane N , N -Dimethylformamide, N , N -One or more of the following: dimethylacetamide, diethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol, glycerol, n-butanol, cyclohexanol, and propylene glycol monomethyl ether acetate; More preferably, the water-soluble organic solvent may be selected from... N methylpyrrolidone, dimethyl sulfoxide, N , N -Dimethylformamide, diethylene glycol monomethyl ether N , N One or more of dimethylacetamide.
[0033] In one embodiment, the cleaning composition may further include corrosion inhibitors, reducing agents, and / or surfactants; Preferably, based on the total weight of the cleaning composition, the cleaning composition includes 0.1 wt% to 10 wt% of a corrosion inhibitor; 0.1 wt% to 10 wt% reducing agent; and / or Surfactants ranging from 0.1 wt% to 10 wt%.
[0034] In the cleaning composition, corrosion inhibitors can reduce the corrosion of metals by the cleaning composition; reducing agents can reduce the oxidation potential of the solution and synergistically reduce the corrosion of the substrate by halogens with metal salts; surfactants can promote the dispersibility and stability of the components in the cleaning agent.
[0035] In one embodiment, the corrosion inhibitor may be a compound containing heteroatoms, wherein the heteroatoms are selected from one or more of oxygen atoms, nitrogen units, sulfur atoms, and phosphorus atoms; Preferably, the corrosion inhibitor is selected from one or more of benzotriazole, sorbitol, and L-cysteine.
[0036] In one specific embodiment, the reducing agent may be selected from one or more of thiourea dioxide, oxalic acid, and ascorbic acid.
[0037] In one specific embodiment, the surfactant may include cationic surfactants, anionic surfactants, and nonionic surfactants; Preferably, the surfactant may be selected from one or more of the following: 3,5-dimethylhex-1-yn-3-ol, lauryl ether phosphate, cocoyl diethanolamide, cocamidopropyl betaine, acetone oxime, lauryl propylamine oxide, monoglyceride, span, and polyoxy-15-hydroxystearate. More preferably, the surfactant may be selected from one or more of the following: lauryl ether phosphate, span, and cocoyl diethanolamide.
[0038] This application also provides a method for preparing the aforementioned anti-corrosion cleaning composition, comprising: A metal salt compound, a chelating agent, and optionally a corrosion inhibitor, a reducing agent, and a surfactant are dissolved in an organic solvent to form a mixture. A synergist is then added to the mixture to obtain the corrosion-resistant cleaning composition.
[0039] This application further provides a method for cleaning electronic devices, including: Electronic devices are cleaned using the aforementioned anti-corrosion cleaning composition or the anti-corrosion cleaning composition prepared according to the aforementioned preparation method. Preferably, the electronic device comprises one or more of the following materials: silicon, sapphire, silicon carbide, aluminum, copper, gold, silver, nickel, titanium, tungsten, stainless steel, silicon dioxide, silicon nitride, gallium nitride, titanium nitride, aluminum nitride, high-k dielectric layer, and low-k dielectric layer.
[0040] In one specific embodiment, the electronic device may be a photovoltaic cell, an LED chip, a microelectromechanical chip, a power chip, a memory chip, a PCB board, etc.
[0041] This application does not impose any special restrictions on the source of any raw materials; they can be commercially available.
[0042] The formulations of Examples 1-23 and Comparative Examples 1-3 are shown in Tables 1-3 below.
[0043]
[0044]
[0045]
[0046] Preparation method: According to the formulation, a metal salt compound, a chelating agent, and optionally a corrosion inhibitor, a reducing agent, and optionally a surfactant are dissolved in an organic solvent to form a mixture. A synergist amine compound and water are slowly added to the mixture, and after thorough mixing, the corrosion-resistant cleaning composition is obtained.
[0047] Experimental example: Aging corrosion tests were conducted on Examples 1-23 and Comparative Examples 1-3. The specific experimental methods are as follows: Test piece: Microscopic image of the substrate to be cleaned after dry etching process, as shown below. Figure 1 As shown.
[0048] Dielectric layer thickness testing: The metal layer was tested with a four-probe instrument to measure the change in resistance before and after corrosion, and the thickness change was calculated; the passivation layer was tested with an ellipsometry to measure the change in film thickness before and after corrosion, and the results were recorded.
[0049] Corrosion Test I: A certain amount of halide ions was added to the formulation solutions of Examples 1-11 and Comparative Examples 1-3 (the aging corrosion conditions used in this test were: 50 ppm F). - ions / Cl - (Ions and their combinations), and at the same time, the solution is placed in a 90℃ oil bath. After the temperature stabilizes, the dielectric layer test piece is immersed in the solution for 30 minutes, then taken out, rinsed with deionized water for 30 seconds and dried with nitrogen gas, and then the dielectric layer film thickness is tested.
[0050] Corrosion Test II: A certain amount of halide ions was added to the formulation solutions of Examples 1, 12-20 and Comparative Examples 1-3 (the aging corrosion conditions used in this test were: 200 ppm F). - ions / Cl - (Ions and their combinations), and at the same time, the solution is placed in a 90℃ oil bath. After the temperature stabilizes, the dielectric layer test piece is immersed in the solution for 30 minutes, then taken out, rinsed with deionized water for 30 seconds and dried with nitrogen gas, and then the dielectric layer film thickness is tested.
[0051] Cleaning Test I: Immerse the cleaning test piece in the 90℃ formulation solution, remove it after 20 minutes, rinse with deionized water for 30 seconds and dry with nitrogen gas, and observe the results under a microscope.
[0052] Cleaning Test II: Immerse the cleaning test piece in the 90℃ formulation solution, remove it after 5 minutes, rinse with deionized water for 30 seconds and dry with nitrogen gas, and observe the results under a microscope.
[0053] Microscopic observation: Use a microscope to observe the test pieces before and after cleaning, and observe the pitting corrosion and cleanliness of the test substrate surface after cleaning.
[0054] The test results are shown in Tables 4-6.
[0055]
[0056]
[0057]
[0058] The results in Tables 4 and 5 show that the wafers cleaned with the cleaning solution containing alkali metal salts, as described in this application, significantly reduced the corrosion rate of halogens on Al, Ti, and SiO2 while maintaining the cleanliness of the cleaned wafers. Furthermore, the formulation with added surfactants, chelating agents, and corrosion inhibitors further reduced the corrosion rate of halogens on Al, improving the weather resistance of the devices. In Comparative Example 1, without the addition of metal salt compounds, Tables 4 and 5 show severe pitting corrosion in both corrosion test I (low halide ion concentration, 50 ppm) and corrosion test II (high halide ion concentration, 200 ppm). This demonstrates that the addition of metal salt compounds to the cleaning composition in this application effectively reduces the corrosion of metals by halogens. Similarly, in Comparative Example 2, without the addition of water, severe pitting corrosion occurred in corrosion test I (Table 4) and corrosion test II (Table 5). In Comparative Example 3, the addition of 85 wt% water resulted in severe corrosion in Corrosion Test I, even with a low halide ion concentration (50 ppm), with a corrosion rate significantly higher than that of the Examples and other comparative examples. Compared to Example 13, the cleaning solutions of Examples 21-23 used different reducing agents to replace the surfactant in Example 13. As shown in Table 6, the wafers cleaned using the cleaning solutions containing reducing agents (Examples 21-23) of this application show a significant reduction in cleaning time and efficiency. This demonstrates that by controlling the water content in the formulation to 1 wt%~10 wt%, this application achieves a formulation with excellent cleaning performance and reduced halogen corrosion.
[0059] Using the formulations of Examples 1-23 of this application can reduce the corrosion of metals by halogens. Taking Example 4 and Comparative Example 1 as examples, a comparison is made. Figure 2 and Figure 3 It can be seen that after cleaning with the formulation of Example 4, the dielectric layer and metal structure on the test substrate remained intact, and similar results were obtained with the formulations of other examples; while when cleaning with the formulation of Comparative Example 1, the metal in the middle region of the test substrate showed obvious corrosion. Therefore, the cleaning results of the examples and comparative examples show that adding alkali metal salts can effectively improve the corrosion resistance of the solution.
[0060] The present application has been described above with reference to preferred embodiments; however, these embodiments are merely exemplary and illustrative. Various substitutions and modifications can be made to the present application based on these embodiments, all of which fall within the protection scope of the present application.
Claims
1. A corrosion-resistant cleaning composition, characterized in that, The cleaning composition includes: 0.01 wt%~10 wt% metal salt compounds, 0.1 wt%~10 wt% chelating agent 1 wt%~50 wt% synergist, and The remaining organic solvent, based on the total weight of the cleaning composition, The synergist includes amine compounds and water; The metal salt compound is selected from one or more of sodium acetate, potassium acetate, lithium carbonate, and aluminum sulfate; The chelating agent is a compound containing coordinating atoms, which are selected from one or more of oxygen atoms, nitrogen units, sulfur atoms, and phosphorus atoms.
2. The anti-corrosion cleaning composition according to claim 1, characterized in that, The cleaning composition comprises 1 wt% to 10 wt%, preferably 1 wt% to 5 wt% water, based on the total weight of the cleaning composition.
3. The anti-corrosion cleaning composition according to claim 1, characterized in that, The amine compound is selected from one or more of primary amines, secondary amines, tertiary amines, and organic ammonium salts; Preferably, the amine organic compound is selected from one or more of triethanolamine, diethanolamine, tetramethylammonium hydroxide, ethanolamine, and diethylamine.
4. The anti-corrosion cleaning composition according to claim 1, characterized in that, The chelating agent is selected from one or more of catechol, phthalic acid, and ethylenediaminetetraacetic acid.
5. The anti-corrosion cleaning composition according to claim 1, characterized in that, The organic solvent is a water-soluble organic solvent; Preferably, the organic solvent is selected from... N -Methylpyrrolidone, N -Ethylpyrrolidone, dimethyl sulfoxide, sulfolane N , N -Dimethylformamide, N , N -One or more of the following: dimethylacetamide, diethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol, glycerol, n-butanol, cyclohexanol, and propylene glycol monomethyl ether acetate; More preferably, the water-soluble organic solvent is selected from... N methylpyrrolidone, dimethyl sulfoxide, N , N -Dimethylformamide, diethylene glycol monomethyl ether N , N One or more of dimethylacetamide.
6. The anti-corrosion cleaning composition according to claim 1, characterized in that, The cleaning composition also includes corrosion inhibitors, reducing agents and / or surfactants; Preferably, based on the total weight of the cleaning composition, the cleaning composition includes 0.1 wt% to 10 wt% of a corrosion inhibitor; 0.1 wt% to 10 wt% reducing agent; and / or Surfactants ranging from 0.1 wt% to 10 wt%.
7. The anti-corrosion cleaning composition according to claim 6, characterized in that, The corrosion inhibitor is a compound containing heteroatoms, wherein the heteroatoms are selected from one or more of oxygen atoms, nitrogen units, sulfur atoms, and phosphorus atoms; Preferably, the corrosion inhibitor is selected from one or more of benzotriazole, sorbitol, and L-cysteine.
8. The anti-corrosion cleaning composition according to claim 6, characterized in that, The reducing agent is selected from one or more of thiourea dioxide, oxalic acid, and ascorbic acid.
9. A method for preparing the anti-corrosion cleaning composition according to any one of claims 1 to 8, characterized in that, The method includes: A metal salt compound, a chelating agent, and optionally a corrosion inhibitor, a reducing agent, and a surfactant are dissolved in an organic solvent to form a mixture. A synergist is then added to the mixture to obtain the corrosion-resistant cleaning composition.
10. A method for cleaning electronic devices, characterized in that, The method includes: Electronic devices are cleaned using the anti-corrosion cleaning composition according to any one of claims 1 to 8 or the anti-corrosion cleaning composition prepared according to the preparation method of claim 9; Preferably, the electronic device comprises one or more of the following materials: silicon, sapphire, silicon carbide, aluminum, copper, gold, silver, nickel, titanium, tungsten, stainless steel, silicon dioxide, silicon nitride, gallium nitride, titanium nitride, aluminum nitride, high-k dielectric layer, and low-k dielectric layer.