CN115261858A - Etching solution composition and application thereof - Google Patents

Etching solution composition and application thereof Download PDF

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Publication number
CN115261858A
CN115261858A CN202210944827.2A CN202210944827A CN115261858A CN 115261858 A CN115261858 A CN 115261858A CN 202210944827 A CN202210944827 A CN 202210944827A CN 115261858 A CN115261858 A CN 115261858A
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acid
etching
etching solution
percent
solution composition
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刘功础
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Guangzhou China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Guangzhou China Star Optoelectronics Semiconductor Display Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/02—Local etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/26—Acidic compositions for etching refractory metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32139—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer using masks

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Abstract

The application provides an etching solution composition and application thereof, wherein the etching solution composition comprises the following components in percentage by mass: 15 to 25 percent of oxidant, 0.1 to 5 percent of main chelating agent, 0.1 to 3 percent of auxiliary chelating agent, 0.01 to 3 percent of main corrosion inhibitor, 0.01 to 2 percent of auxiliary corrosion inhibitor, 0.1 to 5 percent of inorganic salt etchant, 0.1 to 5 percent of alcohol stabilizer, 0.01 to 3 percent of fluorine-containing etchant and the balance of solvent. This application can prolong the life of etching solution to 7000ppm, has greatly reduced the cost of etching solution in the manufacturing process, simultaneously, promotes etching homogeneity and etching stability, has improved the etching performance and the security performance of etching solution.

Description

Etching solution composition and application thereof
Technical Field
The application relates to the technical field of display, in particular to an etching solution composition and application thereof.
Background
A microcircuit of a thin film transistor liquid crystal display device (TFT-LCD) is formed through a series of exposure and development processes. Specifically, photoresist (PR) is uniformly coated on a metal film/semiconductor film/insulating film formed on a substrate, a patterned photoresist is formed by development after light irradiation, a portion not covered by the photoresist is etched by dry or wet etching, and finally a patterned film is formed by peeling off the PR, thus the above-mentioned microcircuit is formed. In order to reduce the delay of the electrical signal, the metal film layer is usually selected from copper (Cu) with a low resistivity. In view of poor adhesion (adhesion) of copper to the glass film and the semiconductor layer, and in order to prevent diffusion (diffusion) of Cu into the semiconductor layer, a Barrier metal (Barrier metal) is plated in between, and currently, molybdenum and its alloy (for example, moTi, etc.) are attracting attention. In order to effectively etch such a metal film with a multilayer structure, hydrogen peroxide-based etching solution is commonly used in the industry, however, the service life of the etching solution is short due to decomposition of hydrogen peroxide, which results in high use cost. Generally speaking, stabilizers are divided into two types, including amine-containing compounds and polymer-based agents, but their effectiveness in Cu/MoTi-based etching solution systems is not as good. Therefore, the development of a novel stabilizer is of great significance for prolonging the service life of the Cu/MoTi etching solution.
Disclosure of Invention
The application provides an etching solution composition and application thereof, aiming at solving the technical problem that the service life of the etching solution is short due to decomposition of an oxidant.
The application provides an etching solution composition, which comprises the following components in percentage by mass:
15% -25% of an oxidant;
0.1-5% of main chelating agent;
0.1 to 3 percent of auxiliary chelating agent;
0.01 to 3 percent of main corrosion inhibitor;
0.01 to 2 percent of auxiliary corrosion inhibitor;
0.1 to 5 percent of inorganic salt etching agent;
0.1 to 5 percent of alcohol stabilizer;
fluorine-containing etchant 0.01% -3% and
the balance of solvent.
Optionally, in some embodiments of the present application, the etching solution composition includes the following components in percentage by mass:
17% -23% of an oxidant;
1% -4% of a main chelating agent;
0.5 to 2.0 percent of auxiliary chelating agent;
0.05 to 2 percent of main corrosion inhibitor;
0.1 to 2 percent of auxiliary corrosion inhibitor;
0.1 to 3 percent of inorganic salt etching agent;
0.1 to 3 percent of alcohol stabilizer;
0.01% -1% of fluorine-containing etching agent and
the balance of solvent.
Optionally, in some embodiments herein, the alcoholic stabilizer is selected from: any one or two or more of 1, 2-propanediol, glycerol, diglycerol, triglycerol, glyceraldehyde, dihydroxyacetone, ethylene glycol, diethylene glycol, glycolaldehyde, pentaerythritol, trimethylolethane, xylitol, sorbitol, glucose, 1, 4-butanediol, erythritol, 1,2, 4-butanetriol, 1,2, 3-butanetriol, 1, 6-hexanediol, 1, 2-hexanediol, neopentyl glycol, dipropylene glycol, and trimethylolpropane; and/or, the oxidizing agent is selected from hydrogen peroxide.
Optionally, in some embodiments herein, the primary chelating agent is selected from: any one or two or more of iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylnitroacetic acid, aminotri (methylphosphoric acid), (1-hydroxyethane-1, 1-diene compound) bis (phosphoric acid), ethylenediamine tetra (methylphosphoric acid), diethylenetriaminepenta (methylphosphoric acid), alanine, glutamic acid, aminobutyric acid, and glycine; and/or the auxiliary chelating agent is an organic acid having at least one hydroxyl group and no nitrogen atom.
Optionally, in some embodiments herein, the organic acid is selected from: any one or more of acetic acid, formic acid, butyric acid, citric acid, glycolic acid, oxalic acid, malonic acid, valeric acid, propionic fruit acid, gluconic acid and succinic acid.
Optionally, in some embodiments of the present application, the inorganic salt etchant is selected from any one or two or more of phosphate, hydrogen phosphate, sulfate, and hydrogen sulfate; and/or the fluorine-containing etching agent is selected from one or more of hydrogen fluoride, ammonium fluoride, potassium fluoride, sodium fluoride, ammonium bifluoride, potassium bifluoride and sodium bifluoride.
Optionally, in some embodiments herein, the primary corrosion inhibitor and the secondary corrosion inhibitor are both azole compounds.
Optionally, in some embodiments herein, the azole compound is selected from any one or more of 3-amino-1, 2, 3-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 3-triazole, 4-amino-1, 2, 4-triazole, 5-methyltetrazole, 5-aminotetrazole, imidazole, and pyrazole compounds.
Optionally, in some embodiments of the present application, the etching solution composition further includes: 0.01% -3% of pH regulator, so as to regulate the pH value of the etching solution composition to 2-5.
Correspondingly, the application also provides a use of the etching solution composition in etching a metal layer of a display device, wherein the metal layer is a single-layer metal film or a laminated metal film, and the single-layer metal film is a copper film, a molybdenum film or a molybdenum alloy film; the laminated metal film includes a first molybdenum film, a copper film, and a second molybdenum film, or a first molybdenum alloy film, a copper film, and a second molybdenum alloy film.
The application has at least one or more of the following advantages:
the application provides an etching solution composition, wherein an alcohol stabilizer is added into the composition to capture free radicals in the etching solution and prevent the free radicals from being decomposed due to the attack of the free radicals on an oxidant, so that the decomposition of the oxidant is inhibited, the service life (bathlife) of the etching solution is prolonged, and compared with the etching solution which is added with a polymer or an amine compound as a stabilizer in the prior art, the service life of the etching solution can be prolonged to 7000ppm, and the cost of the etching solution in the production and manufacturing process is greatly reduced; meanwhile, the etching uniformity and the etching stability are improved, and the etching performance and the safety performance of the etching solution are improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a scanning electron micrograph of an etchant composition of example 1 at a copper ion concentration of 7000ppm as provided herein;
FIG. 2 is a Scanning Electron Micrograph (SEM) of the etchant composition of example 2 at a copper ion concentration of 1000 ppm;
FIG. 3 is a scanning electron micrograph at a copper ion concentration of 7000ppm using the etchant composition of example 2 provided herein;
FIG. 4 is a Scanning Electron Micrograph (SEM) of an etchant composition prepared according to comparative example 1 at a copper ion concentration of 6000 ppm;
FIG. 5 is a Scanning Electron Micrograph (SEM) of an etchant composition prepared in comparative example 2 at a copper ion concentration of 6000 ppm;
FIG. 6 is a Scanning Electron Micrograph (SEM) of an etchant composition prepared in comparative example 3, wherein the concentration of Cu ions is 6000 ppm.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application. Furthermore, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the present application, are given by way of illustration and explanation only, and are not intended to limit the present application. In the present application, unless otherwise specified, the use of directional terms such as "upper", "lower", "left" and "right" generally refer to upper, lower, left and right in the actual use or operation of the device, and specifically to the orientation of the drawing figures.
The present application provides an etchant composition and applications thereof, which are described in detail below. It should be noted that the following description of the embodiments is not intended to limit the preferred order of the embodiments of the present application. In the following embodiments, the descriptions of the respective embodiments have respective emphasis, and reference may be made to related descriptions of other embodiments for parts that are not described in detail in a certain embodiment.
Embodiments of the present application provide an etching solution composition. The etching solution composition can etch the multilayer metal film. The metal film exists in the thin film transistor liquid crystal display device, and forms a microcircuit after etching. The structure of the multilayer metal film can comprise a first buffer layer formed on the glass substrate, a copper film layer formed on the first buffer layer and a second buffer layer formed on the copper film layer, wherein the first buffer layer and the second buffer layer are made of molybdenum simple substances or molybdenum alloy film layers, and the copper film layer is made of copper simple substances. The etching solution composition can also etch a single-layer metal film, and the single-layer metal film can be a copper film layer, a molybdenum film layer or a molybdenum alloy film layer, wherein the copper film layer is made of a simple copper substance, the molybdenum film layer is a simple molybdenum substance, and the molybdenum alloy film layer is made of a molybdenum-titanium alloy.
In some embodiments of the present application, the etching solution composition comprises the following components in percentage by mass:
15% -25% of an oxidant;
0.1-5% of main chelating agent;
0.1% -3% of auxiliary chelating agent;
0.01 to 3 percent of main corrosion inhibitor;
0.01 to 2 percent of auxiliary corrosion inhibitor;
0.1 to 5 percent of inorganic salt etching agent;
0.1 to 5 percent of alcohol stabilizer;
0.01% -3% of fluorine-containing etching agent; and
the balance of solvent.
It is understood that within the range of values for each component, each component can take any of the values within the range. The total mass percentage content sum of the oxidant, the main chelating agent, the auxiliary chelating agent, the main corrosion inhibitor, the auxiliary corrosion inhibitor, the inorganic salt etching agent, the alcohol stabilizer, the fluorine-containing etching agent and the solvent is 100 percent. The solvent may be deionized water. According to the embodiment of the application, the components of the etching solution composition are reasonably matched and proportioned, so that the etching solution composition has the advantages of high etching uniformity, high stability, longer service life and the like, and can be better applied to etching of a plurality of metal films.
In some embodiments of the present application, the oxidizing agent is hydrogen peroxide. The hydrogen peroxide can be commercial industrial hydrogen peroxide. The hydrogen peroxide is added into the etching solution composition as an oxidant, so that the strong oxidizing capability can be provided, and the etching rate of the etching solution composition can be improved. It can be understood that the alcohol stabilizer has a good inhibition effect on hydrogen peroxide, and can effectively inhibit the hydrogen peroxide from decomposing, thereby being beneficial to prolonging the service life of the etching liquid composition and reducing the cost of the etching liquid composition. In some embodiments, the hydrogen peroxide may be 15% to 25% by weight. Or any one of 17% to 23%. The end value of the mass percentage content of the hydrogen peroxide can be 16%, 18%, 19%, 20%, 21%, 22% or 24%. As a preferred embodiment, when the mass percentage content of the hydrogen peroxide is any one value in the range of 17-23%, the oxidation capacity and the etching speed of the etching solution composition on the multilayer metal film are improved, the accumulated number of processing pieces is increased, the processing efficiency and the range (margin) of the process liquid crystal amount are further improved, and the device performance is improved.
In some embodiments herein, the alcoholic stabilizer is a polyol. The polyol compound is used as a stabilizer of the etching solution composition, and is beneficial to improving the etching uniformity and the etching stability. For example, in some embodiments, compared with the etching solution containing amine-based compound and polymer-based agent stabilizer commonly used in the related art, the addition of the polyol-based compound improves the etching performance, such as small fluctuation of the line width loss (CD loss) and good stability of the slope (taper) angle, so that the service life (bathlife) of the etching solution composition is increased to 7000ppm, thereby prolonging the service life of the etching solution composition.
It should be noted that, in the related art, commonly used stabilizers include an amine group-containing compound and a polymer reagent, but these two types of stabilizers have poor etching stability in a Cu/MoTi-based etching solution system, and the bathlife is only 4000ppm, resulting in high cost. The application introduces the polyol compound as a stabilizer to capture free radicals in the etching solution so as to prevent the free radicals from attacking the oxidant to cause decomposition of the oxidant, thereby playing a role in inhibiting the decomposition of the oxidant and overcoming the problems of poor etching effect, shortened service life and the like of the etching solution composition caused by the decomposition of the oxidant. On the other hand, the alcohol stabilizer and the chelating agent have better compatibility, and the alcohol stabilizer and the chelating agent can play a synergistic role in inhibiting the decomposition of the oxidant.
In other embodiments, the polyol compound may be selected from any one or two or more of 1, 2-propanediol, glycerol, diglycerol, triglycerol, glyceraldehyde, dihydroxyacetone, ethylene glycol, diethylene glycol, glycolaldehyde, pentaerythritol, trimethylolethane, xylitol, sorbitol, glucose, 1, 4-butanediol, butanetetraol, 1,2, 4-butanetriol, 1,2, 3-butanetriol, 1, 6-hexanediol, 1, 2-hexanediol, neopentyl glycol, dipropylene glycol, and trimethylolpropane. The polyol compound can effectively capture free radicals in the etching solution, and prevent poor etching effect and shortened service life of the etching solution caused by decomposition of an oxidizing agent due to attack of the free radicals on the oxidizing agent. Meanwhile, the polyol compound has good compatibility, and can play a synergistic role with the main chelating agent and the auxiliary chelating agent to inhibit the decomposition of the oxidant.
In other embodiments, the primary chelating agent is an inorganic acid. The inorganic acid may be any one or two or more selected from iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylnitroacetic acid, aminotri (methyl phosphoric acid), (1-hydroxyethane-1, 1-diene compound) bis (phosphoric acid), ethylenediamine tetra (methyl phosphoric acid), diethylenetriaminepenta (methyl phosphoric acid), alanine, glutamic acid, aminobutyric acid, and glycine. The chelating agent can be chelated with metal ions generated in the etching process to passivate the metal ions, inhibit the decomposition of the oxidant and prevent explosion accidents caused by the decomposition and heating of the oxidant so as to ensure the stability of the etching solution composition. The content of the chelating agent in percentage by mass can be any value of 0.1-5% or any value of 1-4%. The chelating agent may also have an end value of 2% or 3%. As a preferable embodiment, when the mass percentage content of the chelating agent is any one of 1% to 4%, the method is favorable for maintaining high etching efficiency and ensuring the stability of the etching solution composition, and further is favorable for improving the bathlife, reducing the cost and having good economic benefit.
In some other embodiments, the auxiliary chelating agent may be an organic acid having at least one hydroxyl group and no nitrogen atom. The organic acid is selected from one or more of acetic acid, formic acid, butyric acid, citric acid, glycolic acid, oxalic acid, malonic acid, valeric acid, propionic tartaric acid, gluconic acid and succinic acid. The auxiliary chelating agent can promote the main chelating agent to maintain the stability of the etching solution composition, and is beneficial to adjusting the etching speed among metal components contained in the film layers of the multi-layer metal film.
In another embodiment, the content of the auxiliary chelating agent may be any one of 0.1% to 3% by mass, or may be any one of 0.5% to 2.0% by mass. The end value of the mass percentage content of the auxiliary chelating agent can also be 1%, 1.5% or 2.5%. As a preferred embodiment, when the mass percentage content of the auxiliary chelating agent is any one of 0.5% to 2.0%, it is advantageous to improve the stability of the etching solution composition.
In other embodiments, the primary corrosion inhibitor may be an azole compound. The azole compound may be any one or two or more selected from the group consisting of 3-amino-1, 2, 3-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 3-triazole, 4-amino-1, 2, 4-triazole, 5-methyltetrazole, 5-aminotetrazole, imidazole, and pyrazole. The azole compound can be combined with metal on the surface of the metal wire to inhibit corrosion of the metal wire caused by the etchant, so that the metal wire is protected from corrosion, the effect of adjusting the Etching Profile is achieved, the critical deviation of the metal wire can be reduced, and the process margin is improved. The azole compound can play a role of a main corrosion inhibitor, and is presumed to be capable of partially slowing the dissolution rate of the metal wiring according to an experimental result and partially inhibiting the copper simple substance from being directly oxidized into copper oxide. The slow release effect of the azole compound is also related to the pH value of the whole system of the etching solution composition.
In other embodiments, the mass percentage of the main corrosion inhibitor may be any one of 0.01% to 3%, and may also be any one of 0.05% to 2%. The end value of the mass content of the main corrosion inhibitor can also be 1%, 1.5% or 2.5%. As a preferable implementation mode, when the mass percentage of the main corrosion inhibitor takes any value of 0.05-2%, the stable etching efficiency is favorably maintained, and the corrosion of the metal wire is inhibited.
In other embodiments, the supplemental corrosion inhibitor may be an azole compound. The azole compound may be any one or two or more of 3-amino-1, 2, 3-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 3-triazole, 4-amino-1, 2, 4-triazole, 5-methyltetrazole, 5-aminotetrazole, imidazole, and pyrazole. The azole compound can be matched with the main corrosion inhibitor, which is beneficial to improving the stability of the etching solution composition and maintaining the etching uniformity, and in addition, the dosage of the main corrosion inhibitor can be reduced, which is beneficial to obtaining a lower etching slope (taper) angle. The Etching efficiency is regulated and controlled by utilizing the auxiliary corrosion inhibitor and the main corrosion inhibitor, so that the stable Etching efficiency can be ensured, the metal wire can be better protected from being corroded, and the effect of regulating the Etching Profile (Etching Profile) is achieved. It should be noted that the main corrosion inhibitor and the auxiliary corrosion inhibitor are compounded by different azole compounds, which is beneficial to regulating and controlling the etching efficiency.
In other embodiments, the mass percentage of the auxiliary corrosion inhibitor may be any one of 0.01% to 2%, and may also be any one of 0.1% to 2%. The mass percentage content of the auxiliary corrosion inhibitor can be 0.5%, 0.15%, 0.17% or 0.18%. In a preferred embodiment, when the mass percentage content of the auxiliary corrosion inhibitor is any one value of 0.1-2%, the auxiliary corrosion inhibitor and the main corrosion inhibitor are promoted to have a better synergistic effect, the stable etching efficiency is maintained, and the corrosion of the wiring is inhibited.
In other embodiments, the inorganic salt etchant may be selected from any one or two or more of phosphate, hydrogen phosphate, sulfate, and hydrogen sulfate. The content of the metal film etching solution is increased during implementation, so that the etching speed of the metal film etching solution is improved, and the effect of adjusting the pH value of the etching solution composition can be achieved. The inorganic salt etchant is most preferably sulfate, which is beneficial to improving the etching speed and improving the engineering efficiency.
In other embodiments, the mass percentage of the inorganic salt etchant may be any one of 0.1% to 5%, and may also be any one of 0.1% to 3%, and the end value of the mass percentage of the inorganic salt etchant may be 0.5%, 1%, 2%, or 4%. In a preferred embodiment, when the inorganic salt etchant accounts for any one value of 0.1-3% by mass, a moderate Etching speed can be provided, so that the Etching Profile (Etching Profile) is good, the engineering efficiency can be improved, and the range (margin) of the process liquid crystal quantity can be increased.
In other embodiments, the fluorine-containing etchant is selected from any one or two or more of hydrogen fluoride, ammonium fluoride, potassium fluoride, sodium fluoride, ammonium bifluoride, potassium bifluoride, and sodium bifluoride. The fluorine-containing etching agent can promote the etching effect on the metal film layer containing molybdenum and molybdenum-containing alloy thereof and reduce the generation of metal residues.
In other embodiments, the fluorine-containing etchant may be any one of 0.01% to 3% by mass, or any one of 0.01% to 1% by mass, and the end of the fluorine-containing etchant may be 0.1%, 1.5% or 2% by mass. As a preferred implementation mode, when the fluorine-containing etching agent takes any one value of 0.01-1% by mass, the etching effect on the molybdenum-containing film layer and the molybdenum alloy film layer is improved, and the damage to the glass substrate under the metal layer can be avoided.
In other embodiments, the etching solution composition further comprises a pH regulator for regulating the pH of the etching solution composition to 2-5, so as to improve the etching performance while ensuring the stability of the etching solution composition. The pH regulator can be one or more of potassium hydroxide, sodium hydroxide and ammonium hydroxide.
In some embodiments, the content of the pH adjuster by mass may be any one of 0.01% to 3%, or 0.1% to 2%, and the end value of the content of the pH adjuster by mass may be 1%, 1.5%, or 2.5%. As a preferred embodiment, when the pH adjuster is 0.1% to 2%, the stability of the etching solution composition is advantageously improved, and the etching rate is advantageously improved.
Embodiments of the present application also provide a use of the etching solution composition in etching a metal layer of a display device, where the metal layer has a structure of a single-layer metal film or a stacked metal film, and the single-layer metal film may be a copper film, a molybdenum film, or a molybdenum alloy film. The laminated metal film includes: the first molybdenum film, the copper film and the second molybdenum film, or the first molybdenum alloy film, the copper film and the second molybdenum alloy film, or the molybdenum alloy film, the copper film and the molybdenum film. The material of the copper film is simple substance copper, the material of the molybdenum film is simple substance molybdenum, and the material of the molybdenum alloy film can be molybdenum-titanium alloy.
In some embodiments, the structure of the display device includes: a laminated structure is formed on a glass substrate, and the laminated structure is a metal layer, a semiconductor film and an insulating film. Wherein, the metal layer includes: the metal film includes a first buffer layer formed on a glass substrate, a copper film layer formed on the first buffer layer, and a second buffer layer formed on the copper film layer, thereby constituting a metal film of a multilayer structure. The first buffer layer and the second buffer layer are made of molybdenum simple substances or molybdenum alloy films, and the copper films are made of copper simple substances. The first buffer layer is arranged between the copper film layer and the glass substrate, so that the bonding performance between the copper film layer and the glass substrate is improved; the second buffer layer is arranged between the copper film layer and the semiconductor film, so that the bonding property between the copper film layer and the semiconductor film is improved, and meanwhile, cu in the copper film layer is prevented from being diffused into the semiconductor film, and the performance of the device is optimized.
The etching solution composition can be used for etching copper-based metal films and multilayer-structured metal films including molybdenum-based metal films. By adopting alcohols as a stabilizer and applying the alcohol as the stabilizer to the etching solution of the Cu/MoTi multilayer metal film, the etching uniformity can be effectively improved, the service life of the etching solution is prolonged, and the better etching performance can be maintained even under the condition of high copper ion concentration.
The technical effects of the present application will be further clarified below with reference to specific examples. As shown in the following table 1, the etching solution compositions of examples 1-2 and comparative examples 1-3 were prepared by mixing the component materials, and the components and the component contents of the examples 1-2 and comparative examples 1-3 are as shown in the following table 1:
Figure BDA0003786921670000101
Figure BDA0003786921670000111
TABLE 1
In the above table, IDA is iminodiacetic acid, ATZ is 5-aminotetrazole, MTZ is 5-methyltetrazole, PEG is polyethylene glycol, TEA is triethanolamine, and CHA is cyclohexylamine.
Test example 1
The etching performance of the etching solution compositions of the examples and the comparative examples in table 1 above was evaluated, and the specific steps were as follows:
MoTi/Cu (thickness) is evaporated on a glass substrate by a grid electrode
Figure BDA0003786921670000112
) Two layers of metal films. A patterned photoresist was formed thereon by a photoresist process, and cut into a 4X3 cm-sized piece with a diamond knife.
1kg of the etching solution composition shown in Table 1 above was placed in a beaker, and etching was carried out when the temperature of the water bath reached the set temperature (32 ℃ C.). The total etching time is over-etched by 30% based on the end point detection (i.e. the copper and molybdenum outside the PR are etched), and the etching time is 140s.
The etched substrate was cleaned and dried, and then the Etching Profile was confirmed by a scanning electron microscope (Etching Profile). In the case of profile (profile), the side etching was observed from the end of the photoresist to the metal film remaining, and the degree of etching residue was observed from below the photoresist, and the results are shown in fig. 1 to 5.
Referring to fig. 1, fig. 1 is a scanning electron microscope photograph of the etchant composition of example 1 at a copper ion concentration of 7000ppm, which shows that the etching performance is good at 7000ppm.
Referring to FIG. 2, FIG. 2 is a scanning electron micrograph of the etchant composition of example 2 at a copper ion concentration of 1000ppm, which shows that the etching performance is good at 1000 ppm.
Referring to FIG. 3, FIG. 3 is a scanning electron micrograph of the etchant composition of example 2 at a copper ion concentration of 7000ppm, which shows good etching performance at 7000ppm.
Referring to FIG. 4, FIG. 4 is a SEM photograph of the etchant composition of comparative example 1 at 6000ppm of Cu ion concentration, showing that the etching performance is deteriorated and not etched through at 6000 ppm.
Referring to FIG. 5, FIG. 5 is a scanning electron micrograph of the etchant composition of comparative example 2 at a copper ion concentration of 6000ppm, showing that the etching performance is deteriorated at 6000ppm without etching through
Referring to FIG. 6, FIG. 6 is a SEM photograph of the etchant composition of comparative example 3 at 6000ppm of Cu ion concentration, showing that the etching performance is deteriorated and not etched through at 6000 ppm.
Test example 2
The service life (Bath life) of the etchant compositions of the respective examples and comparative examples in table 1 above was evaluated.
In general, a hydrogen peroxide-based etching solution undergoes a rapid temperature rise during the decomposition reaction of hydrogen peroxide. In the etching solution compositions of examples 1-2 and comparative examples 1-3, the limit of the service life (bath life) was determined when the rate of change in the line width loss (CD loss) and the slope (taper) exceeded 10% or more after dissolving copper metal at intervals of 1000ppm copper concentration.
Figure BDA0003786921670000121
Figure BDA0003786921670000131
TABLE 2
In the etching solution composition of example 1-2 in table 2, compared with the etching solution composition of comparative example 1-3, the formula of the etching solution composition of example 1-2 adopts the polyol compound as the stabilizer, thereby effectively improving the etching uniformity and the etching stability of the etching solution. Specifically, the etching liquid composition has better etching characteristics, small strip width loss fluctuation, good slope angle stability and longer service life of 7000ppm. Compared with the comparative examples 1 and 2, the etching stability of the conventional polymer or amine compound used as a stabilizer is poor, the lifetime of the bathlife is only 4000ppm, the etching rate is sharply reduced at 6000ppm, and the sample cannot be completely etched under the condition of keeping the same etching time as the example 1-2.
Therefore, the formula of the etching solution composition provided by the application improves the etching uniformity and the etching stability of the etching solution, and has longer service life and reduced production cost.
The foregoing provides a detailed description of the present application, and the principles and embodiments of the present application are described herein using specific examples, which are provided only to help understand the method and the core concept of the present application; meanwhile, for a person skilled in the art, according to the idea of the present application, the specific implementation manner and the application scope may be changed, and in summary, the content of the present specification should not be construed as a limitation to the present application.

Claims (10)

1. The etching solution composition is characterized by comprising the following components in percentage by mass:
15% -25% of an oxidant;
0.1 to 5 percent of main chelating agent;
0.1% -3% of auxiliary chelating agent;
0.01 to 3 percent of main corrosion inhibitor;
0.01 to 2 percent of auxiliary corrosion inhibitor;
0.1 to 5 percent of inorganic salt etching agent;
0.1 to 5 percent of alcohol stabilizer;
0.01% -3% of fluorine-containing etching agent; and
the balance of solvent.
2. The etching solution composition as claimed in claim 1, wherein the etching solution composition comprises the following components in percentage by mass:
17% -23% of an oxidant;
1% -4% of a main chelating agent;
0.5 to 2.0 percent of auxiliary chelating agent;
0.05 to 2 percent of main corrosion inhibitor;
0.1 to 2 percent of auxiliary corrosion inhibitor;
0.1 to 3 percent of inorganic salt etching agent;
0.1 to 3 percent of alcohol stabilizer;
0.01% -1% of fluorine-containing etching agent; and
the balance of solvent.
3. The etching solution composition according to any one of claims 1 to 2, wherein the alcohol stabilizer is selected from the group consisting of: any one or two or more of 1, 2-propanediol, glycerol, diglycerol, triglycerol, glyceraldehyde, dihydroxyacetone, ethylene glycol, diethylene glycol, glycolaldehyde, pentaerythritol, trimethylolethane, xylitol, sorbitol, glucose, 1, 4-butanediol, erythritol, 1,2, 4-butanetriol, 1,2, 3-butanetriol, 1, 6-hexanediol, 1, 2-hexanediol, neopentyl glycol, dipropylene glycol, and trimethylolpropane; and/or
The oxidizing agent is selected from hydrogen peroxide.
4. The etching solution composition according to any one of claims 1 to 2,
the primary chelating agent is selected from: any one or two or more of iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylnitroacetic acid, aminotri (methyl phosphoric acid), (1-hydroxyethane-1, 1-diene compound) bis (phosphoric acid), ethylenediamine tetra (methyl phosphoric acid), diethylenetriaminepenta (methyl phosphoric acid), alanine, glutamic acid, aminobutyric acid, and glycine; and/or
The auxiliary chelating agent is an organic acid having at least one hydroxyl group and no nitrogen atom.
5. The etching solution composition according to claim 4,
the organic acid is selected from: any one or more of acetic acid, formic acid, butyric acid, citric acid, glycolic acid, oxalic acid, malonic acid, valeric acid, propionic fruit acid, gluconic acid and succinic acid.
6. The etching solution composition according to any one of claims 1 to 2,
the inorganic salt etchant is selected from one or more than two of phosphate, hydrogen phosphate, sulfate and hydrogen sulfate; and/or
The fluorine-containing etching agent is selected from one or more of hydrogen fluoride, ammonium fluoride, potassium fluoride, sodium fluoride, ammonium bifluoride, potassium bifluoride and sodium bifluoride.
7. The etching solution composition according to any one of claims 1 to 2,
the main corrosion inhibitor and the auxiliary corrosion inhibitor are azole compounds.
8. The etching solution composition according to claim 7,
the azole compound is selected from any one or more than two of 3-amino-1, 2, 3-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 3-triazole, 4-amino-1, 2, 4-triazole, 5-methyltetrazole, 5-aminotetrazole, imidazole and pyrazole compounds.
9. The etching solution composition according to any one of claims 1 to 2, further comprising: 0.01% -3% of pH regulator to regulate the pH value of the etching solution composition to 2-5.
10. Use of the etching solution composition according to any one of claims 1 to 9 for etching a metal layer of a display device, the metal layer being a single-layer metal film or a laminated metal film, the single-layer metal film being a copper film, a molybdenum film or a molybdenum alloy film; the laminated metal film includes a first molybdenum film, a copper film, and a second molybdenum film, or a first molybdenum alloy film, a copper film, and a second molybdenum alloy film.
CN202210944827.2A 2022-08-08 2022-08-08 Etching solution composition and application thereof Pending CN115261858A (en)

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CN114250469A (en) * 2020-09-24 2022-03-29 深圳新宙邦科技股份有限公司 Etching solution composition and preparation method thereof
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