CN115786916A - Copper etching solution and preparation method thereof, and etching method of glass substrate copper - Google Patents
Copper etching solution and preparation method thereof, and etching method of glass substrate copper Download PDFInfo
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- CN115786916A CN115786916A CN202211649155.9A CN202211649155A CN115786916A CN 115786916 A CN115786916 A CN 115786916A CN 202211649155 A CN202211649155 A CN 202211649155A CN 115786916 A CN115786916 A CN 115786916A
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Abstract
The invention discloses a copper etching solution, a preparation method thereof and a glass substrate copper etching method, and belongs to the technical field of semiconductor display. The copper etching solution comprises, by mass, 1-15% of inorganic acid, 4-10% of peroxide, 4-10% of organic acid and/or salt thereof, 0.5-5.0% of chelating agent, 0.05-0.5% of etching control agent, 0.1-0.5% of surfactant, 0.1-1.0% of stabilizer and the balance of water; the organic acid comprises a first organic acid and a second organic acid; wherein the stability constant lg beta n of the first organic acid and the copper is less than or equal to 10, and the stability constant lg beta n of the second organic acid and the copper is 14-20. The copper etching liquid is especially suitable for etching copper with the thickness of 4-10 mu m, can obtain etching morphology meeting requirements, can effectively control etching rate and loss of critical dimension of patterns, has large etching capacity, and has wider application prospect.
Description
Technical Field
The invention relates to the technical field of semiconductor display, in particular to a copper etching solution and a preparation method thereof, and a glass substrate copper etching method.
Background
The Mini/Micro LED direct display technology is considered as an ultimate display scheme due to the advantages of self-luminescence, high efficiency, low power consumption, high integration, high stability and all-weather operation. COG (chip on glass) means that an LED chip is directly die-bonded to a glass substrate, and display is realized by TFT (thin film transistor) driving. Compared with COB (chip on board), COG has the characteristics of smaller volume, simplified process and the like, and is easier to simplify, miniaturize and highly integrate. More importantly, COG is based on a glass substrate process, and adopts photolithography, semiconductors and advanced copper processes, so that a hyperfine TFT driving structure can be obtained on a large area.
At present, the thickness of a glass-based copper film is between 200nm and 4.5 mu m, and the thickness of the copper film is thicker and thicker (6 to 10 mu m) along with higher requirements on heat dissipation and electric conductivity. From Micro LED technology perspective, the future pixel pitch is already below P1, even below P0.5. Meanwhile, the size of the Micro LED crystal particles will go from 100 microns to 10 microns. At the same time, the line width and pitch of copper have evolved to be smaller and smaller.
Due to the design of the ultra-fine circuit pattern, the requirements on the etching effects such as the side etching and the like are higher and higher; in a traditional hydrogen peroxide etching system, the stability of the system is reduced and the etching performance is deteriorated due to the increase of the content of copper ions.
In general, copper is etched by an etching system using a metal salt such as copper chloride or ferric trichloride, but this has a problem of difficulty in wastewater treatment and has a large etching CD bias; the copper etching system of sulfuric acid and hydrogen peroxide which is commonly used is also applied to the copper etching of a mini/micro LED, and has some problems, such as:
(1) Too fast or too slow an etch rate;
(2) The side etching of the circuit with the thickness of 4-10 mu m is difficult to control;
(3) And because the thickness of the copper is 4-10 mu m, compared with the thickness of the conventional copper about 600nm, the thickness of the copper is more than 6 times that of the conventional product, and the product with the same area has more copper ion content dissolved out in the etching process and small etching capacity, so that the production requirement is difficult to meet.
In view of the above, the present invention is especially proposed
Disclosure of Invention
An object of the present invention is to provide a copper etching solution to solve the above-mentioned problems.
The second objective of the present invention is to provide a method for preparing the copper etching solution.
The present invention also provides a method for etching copper on a glass substrate using the copper etchant.
The application can be realized as follows:
in a first aspect, the present application provides a copper etching solution, which comprises, by mass, 1 to 15% of an inorganic acid, 4 to 10% of a peroxide, 4 to 10% of an organic acid and/or a salt thereof, 0.5 to 5.0% of a chelating agent, 0.05 to 0.5% of an etching control agent, 0.1 to 0.5% of a surfactant, 0.1 to 1.0% of a stabilizer, and the balance being water;
the organic acid comprises a first organic acid and a second organic acid; wherein the stability constant lg beta n of the first organic acid and the copper is less than or equal to 10, and the stability constant lg beta n of the second organic acid and the copper is 14-20.
In an alternative embodiment, the copper etching solution comprises 3-10% of an inorganic acid, 5-8% of a peroxide, 4-7% of an organic acid and/or a salt thereof, 1.5-3.5% of a chelating agent, 0.1-0.3% of an etching control agent, 0.2-0.4% of a surfactant, and 0.3-0.6% of a stabilizer, with the balance being water.
In an alternative embodiment, the first organic acid is a nitrogen atom-free organic acid having at least one or more carboxyl groups.
In alternative embodiments, the first organic acid comprises at least one of a monocarboxylic acid and a dicarboxylic acid; wherein the monocarboxylic acid of the first organic acid comprises at least one of formic acid, butyric acid, benzoic acid, glycolic acid and lactic acid; and/or the dicarboxylic acid in the first organic acid comprises at least one of oxalic acid, malonic acid, succinic acid, tartaric acid and malic acid.
In an alternative embodiment, the first organic acid comprises at least one of lactic acid, oxalic acid, and tartaric acid.
In an alternative embodiment, the second organic acid is an organic acid containing a nitrogen atom.
In alternative embodiments, the second organic acid comprises at least one of a monocarboxylic acid, a dicarboxylic acid, and a polycarboxylic acid; wherein the monocarboxylic acid of the second organic acid comprises at least one of glutamic acid and arginine; and/or, the dicarboxylic acid of the second organic acid comprises iminodiacetic acid; and/or, the polycarboxylic acid comprises at least one of nitrilotriacetic acid and ethylenediaminetetraacetic acid.
In an alternative embodiment, the second organic acid comprises at least one of glutamic acid, iminodiacetic acid, and ethylenediaminetetraacetic acid.
In alternative embodiments, the inorganic acid is phosphoric acid; and/or the peroxide is hydrogen peroxide.
In an alternative embodiment, the chelating agent comprises an organoalkanolamine compound.
In an alternative embodiment, the chelating agent comprises at least one of monoethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine, diglycolamine, and 2-amino-2-methylpropanol.
In an alternative embodiment, the chelating agent is triethanolamine.
In an alternative embodiment, the etching control agent is a tetrazole compound, and the structure formula of the tetrazole compound is as follows:
wherein R is selected from H and CH 3 And NH 3 At least one of (1).
In an alternative embodiment, the etch control agent includes at least one of tetrazole, 5-methyl tetrazole, and 5-amino tetrazole.
In an alternative embodiment, the etch control agent includes at least one of 5-methyl tetrazole and 5-amino tetrazole.
In an alternative embodiment, the surfactant is a block polyether type nonionic surfactant; and/or, the stabilizer comprises at least one of phenyl urea, cyclohexylamine, 1-propanol, and ethylene glycol butyl ether.
In an alternative embodiment, the block polyether is a polyether containing EO-PO-EO blocks.
In an alternative embodiment, the block polyether nonionic surfactant has a molecular weight of 2000 to 5000.
In an alternative embodiment, the stabilizer is phenylurea.
In a second aspect, the present application provides a method for producing a copper etching liquid as in any one of the preceding embodiments, comprising: the components are mixed.
In a third aspect, the present application provides a method for etching copper on a glass substrate, comprising the steps of: the copper etching solution of any one of the preceding embodiments is used to etch copper on a glass substrate.
In an alternative embodiment, the thickness of the copper to be etched is 4-10 μm.
In an alternative embodiment, the etching is performed at 25-40 deg.C for 3-5min.
In an alternative embodiment, the temperature of the etch is 25-30 ℃.
The beneficial effect of this application includes:
in the present application, peroxide is used primarily as the main component of the oxide etching metal; the inorganic acid can play a role in enhancing the oxidation capacity of the peroxide; the first organic acid and/or the salt thereof can maintain the acidity of the etching solution, and the stability constant of a complex formed by the first organic acid and Cu (II) is not high, so that the activation energy of the deposition reaction is low, the triggering speed is high, and the rapid etching of copper is facilitated; the second organic acid and/or the salt thereof has a complexing function and improves the etching performance; on one hand, the etching control agent can prevent the decomposition of hydrogen peroxide caused by the accumulation of copper ions in the etching solution and influence the stability of the etching solution, and on the other hand, the generated chelate is adsorbed on the copper surface, so that the etching rate of the chelate is effectively controlled, the loss of the critical dimension of the pattern is reduced, and the stability of the surface profile is maintained; the chelating agent has stronger complexing ability to copper, reduces the risk of decomposing hydrogen peroxide by free copper ions, and prolongs the service life of the etching solution; the pH value of the etching solution can be adjusted, the etching rate of copper can be controlled and stabilized, the etching life of copper can be prolonged, and the etched circuit can obtain good etching appearance; the surfactant can reduce surface tension, improve the wettability of the etching solution to the substrate surface and improve the permeability of the etching solution to the high part in the substrate structure, so that the etching solution fully contacts the copper layer, the etching initiation reaction is accelerated, and the etching uniformity is better.
The copper etching liquid is especially suitable for etching copper with the thickness of 4-10 mu m, can obtain etching morphology meeting requirements, can effectively control etching rate and loss of critical dimension of patterns, has large etching capacity, and has wider application prospect.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a detailed description of the copper etching solution and the preparation method thereof and the etching method of copper on a glass substrate provided by the present application.
The application provides a copper etching solution, which comprises, by mass, 1-15% of an inorganic acid, 4-10% of a peroxide, 4-10% of an organic acid and/or a salt thereof, 0.5-5.0% of a chelating agent, 0.05-0.5% of an etching control agent, 0.1-0.5% of a surfactant, 0.1-1.0% of a stabilizer, and the balance of water.
The mass percentage of the inorganic acid may be, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, or the like, and may be any other value within a range of 1 to 15%.
The peroxide may be, for example, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, etc., by mass, or any other value within the range of 4-10%.
The mass percentage of the organic acid and/or a salt thereof may be, for example, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, or the like, and may be any other value within a range of 4 to 10%.
The mass percentage of the chelating agent may be, for example, 0.5%, 1%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, or the like, or may be any other value within the range of 0.5 to 5.0%.
The mass percentage of the etching control agent may be, for example, 0.05%, 0.10%, 0.15%, 0.20%, 0.25%, 0.30%, 0.35%, 0.40%, 0.45%, 0.5%, or the like, or may be any other value within a range of 0.05 to 0.5%.
The mass percentage of the surfactant may be, for example, 0.1%, 0.15%, 0.20%, 0.25%, 0.30%, 0.35%, 0.40%, 0.45%, 0.5%, or the like, or may be any other value within a range of 0.1 to 0.5%.
The mass percentage of the stabilizer may be, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, or the like, or may be any other value within the range of 0.1 to 1.0%.
<xnotran> , 3-10% ( 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% 10% ) , 5-8% ( 5%, 5.5%, 6%, 6.5%, 7%, 7.5% 8% ) , 4-7% ( 4%, 4.5%, 5%, 5.5%, 6%, 6.5% 7% ) / , 1.5-3.5% ( 1.5%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2% 3.5% ) , 0.1-0.3% ( 0.1%, 0.12%, 0.15%, 0.18%, 0.2%, 0.22%, 0.25%, 0.28% 0.3% ) , 0.2-0.4% ( 0.2%, 0.22%, 0.24%, 0.26%, 0.28%, 0.3%, 0.32%, 0.34%, 0.36%, 0.38 0.4% ) 0.3-0.6% ( 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55% 0.6% ) , . </xnotran>
Under the preferable proportioning scheme, a better copper etching effect can be obtained.
In this application, the inorganic acid may function to enhance the oxidizing ability of the peroxide. Specifically, the inorganic acid is phosphoric acid, which is a medium-strong acid and has a better etching performance on the copper film.
Hydrogen peroxide is used as peroxide to oxidize and etch copper.
Organic acids and/or salts thereof are understood to mean: the organic acid alone, or a salt corresponding to the organic acid alone (referred to as an organic acid salt for short), or a mixture of an organic acid and a salt of the organic acid.
In the present application, the organic acid includes a first organic acid and a second organic acid, and the organic acid salt is a salt (e.g., sodium salt, etc.) corresponding to the first organic acid and a salt (e.g., sodium salt, etc.) corresponding to the second organic acid, respectively.
Wherein the first organic acid has a stability constant lg β n of 10 or less (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, etc., or other constants within a range of 10 or less), and the second organic acid has a stability constant lg β n of 14 to 20 (e.g., 14, 15, 16, 17, 18, 19, or 20, etc., or other constants within a range of 14 to 20).
The first organic acid and/or the salt thereof with the characteristics can adjust the pH value of the etching solution and maintain the acidity of the etching solution, and the stability constant of a complex formed by the first organic acid and the salt of the first organic acid and the Cu (II) is not high, so that the activation energy of the etching reaction is low, the trigger speed is high, and the copper can be quickly etched under the coordination of the block polyether. The second organic acid and/or the salt thereof with the characteristics can play a complexing function, improve the copper dissolving amount, improve the etching performance and improve the etching stability.
In some alternative embodiments, the first organic acid is an organic acid containing no nitrogen atom and having at least one or more carboxyl groups.
Specifically, the first organic acid may include at least one of a monocarboxylic acid and a dicarboxylic acid. Wherein the monocarboxylic acid of the first organic acid may comprise at least one of formic acid, butyric acid, benzoic acid, glycolic acid and lactic acid; the dicarboxylic acid of the first organic acid may include at least one of oxalic acid, malonic acid, succinic acid, tartaric acid, and malic acid.
In some preferred embodiments, the first organic acid comprises at least one of lactic acid, oxalic acid, and tartaric acid.
In some alternative embodiments, the second organic acid is an organic acid containing a nitrogen atom.
Specifically, the second organic acid may include at least one of monocarboxylic acid, dicarboxylic acid, and polycarboxylic acid (tri-and tri-or higher). Wherein the monocarboxylic acid of the second organic acid may comprise at least one of glutamic acid and arginine; the dicarboxylic acid of the second organic acid comprises iminodiacetic acid; the polycarboxylic acid includes at least one of nitrilotriacetic acid and ethylenediaminetetraacetic acid.
In some preferred embodiments, the second organic acid comprises at least one of glutamic acid, iminodiacetic acid, and ethylenediaminetetraacetic acid.
The second organic acid and/or the salt thereof can effectively chelate metal ions by utilizing a carboxyl oxygen coordination atom, reduce the invasion of an etching solution and the over-etching attack to copper in the etching process, and ensure that the etching solution has a wider operation window and meets the required critical dimension loss.
For reference, the mass ratio of the first organic acid species (first organic acid and/or salt thereof) to the second organic acid species (second organic acid and/or salt thereof) may be 1.
In the present application, the chelating agent includes an organic alcohol amine compound, and may illustratively include at least one of monoethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine, diglycolamine, and 2-amino-2-methylpropanol.
In some preferred embodiments, the chelating agent is triethanolamine.
The chelating agent has strong complexing ability on copper, can reduce the decomposition risk of free copper ions on hydrogen peroxide, and prolongs the service life of the etching solution; and the pH value of the etching solution can be adjusted, and the etching rate of copper is stabilized, so that the etching profile meeting the requirement can be obtained.
In the present application, the etching control agent is a tetrazole compound, and the structural formula of the tetrazole compound is as follows:
wherein R is selected from H and CH 3 And NH 3 At least one of (1).
Illustratively, the etching control agent may include at least one of tetrazole, 5-methyltetrazole, and 5-aminotetrazole.
In some preferred embodiments, the etch control agent includes at least one of 5-methyl tetrazole and 5-amino tetrazole.
The tetrazole substance belongs to a nitrogen heterocyclic compound containing (rich), the substance is relatively stable because 5 atoms on the ring form a large pi bond, the five-membered ring structure is close to pentagon, and the whole group has good coplanarity. The polydentate ligand with multiple coordination sites can be used as a chelating ligand and a bridging ligand, has a flexible, various and colorful coordination mode, and particularly introduces various substituent groups on the 5-position of 5-substituted tetrazole, thereby greatly enriching the coordination mode of the tetrazole ligand. Forming coordination compound with copper to be adsorbed on the surface of copper to prevent further etching of copper, effectively controlling the etching rate of the whole copper, and maintaining the stable etching performance of the etching solution in each stage of use, thereby obtaining ideal etching appearance. In view of the requirements of water solubility and the like, 5-methyltetrazole and/or 5-aminotetrazole are preferably adopted.
In the application, the surfactant is a segmented polyether nonionic surfactant to reduce surface tension, so that the etching solution fully contacts a copper layer, and the etching uniformity is better.
Specifically, the block polyether is a polyether containing an EO-PO-EO block, and illustratively may include at least one of Pluronic PE3100, pluronic PE6100, pluronic PE6400, RPE1740, pluronic PE6200, and Pluronic PE8100, and preferably includes at least one of Pluronic PE6100, pluronic PE6200, and Pluronic PE 8100.
The block polyether is matched with the first organic acid and/or the salt thereof, so that the copper can be etched quickly.
In an alternative embodiment, the molecular weight of the block polyether nonionic surfactant is from 2000 to 5000.
It should be noted that if the molecular weight of the surfactant is too large, foaming properties are too strong; if the molecular weight of the surfactant is too small, the wettability and surface tension may be insufficient.
In the present application, the stabilizer may include at least one of phenylurea, cyclohexylamine, 1-propanol, and ethylene glycol butyl ether, and preferably includes (is) phenylurea.
The stabilizer can improve the stability of peroxide and the service life of the etching solution.
In the present application, peroxide is used primarily as the main component of the oxide etching metal; the inorganic acid can enhance the oxidizing ability of the peroxide; the first organic acid and/or the salt thereof can maintain the acidity of the etching solution, and the stability constant of a complex formed by the first organic acid and Cu (II) is not high, so that the activation energy of the deposition reaction is low, the triggering speed is high, and the rapid etching of copper is facilitated; the second organic acid and/or the salt thereof has a complexing function and improves the etching performance; the etching control agent can prevent the decomposition of hydrogen peroxide caused by the accumulation of copper ions in the etching solution and influence the stability of the etching solution on the one hand, and on the other hand, the generated chelate is adsorbed on the copper surface, so that the etching rate of the chelate is effectively controlled, the loss of the critical dimension of the pattern is reduced, and the stability of the surface profile is maintained; the chelating agent has stronger complexing ability to copper, reduces the risk of decomposing hydrogen peroxide by free copper ions, and prolongs the service life of the etching solution; the pH value of the etching solution can be adjusted, the etching rate of copper can be controlled and stabilized, the etching life of copper can be prolonged, and the etched circuit can obtain good etching appearance; the surfactant can reduce surface tension, improve the wettability of the etching solution to the substrate surface and improve the permeability of the etching solution to the high part in the substrate structure, so that the etching solution fully contacts the copper layer, the etching initiation reaction is accelerated, and the etching uniformity is better.
Correspondingly, the application also provides a preparation method of the copper etching solution, namely, the components are mixed.
Preferably, the mixing process can be performed with stirring to accelerate dissolution, thereby forming a uniform etching solution.
In addition, the application also provides an etching method of the glass substrate copper, which comprises the following steps: and etching the copper on the glass substrate by using the copper etching solution.
The copper etching solution provided by the application is particularly suitable for etching copper with the thickness of 4-10 mu m. Illustratively, the thickness of the copper to be etched may be 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, or the like, and may also be any other value in the range of 4-10 μm.
By etching copper with the thickness of 4-10 μm with the etching solution, not only can excellent etching morphology be obtained, but also the etching rate and the smaller side amount can be effectively controlled, and the etching capacity is large.
For reference, the etching can be performed at 25-40 deg.C (e.g., 25 deg.C, 30 deg.C, 35 deg.C, or 40 deg.C, etc.) for 3-5min (e.g., 3min, 3.5min, 4min, 4.5min, or 5min, etc.). Preferably, the temperature of the etching is 25-30 ℃.
The etching is carried out at the preferable temperature, so that the decomposition of hydrogen peroxide is not caused, and the whole etching process can be stably controlled.
In the specific operation, the piece to be etched with a copper layer thickness of 4-10 μm is placed in the copper etching solution and etched under the above conditions. The etching morphology meeting the requirements can be obtained through the method, and the etching performance is excellent.
The features and properties of the present invention are described in further detail below with reference to examples.
Examples 1 to 9
Examples 1 to 9 correspondingly provide 9 copper etching solutions, which were prepared in the same manner by mixing an oxidizing agent, an inorganic acid, an organic acid, an etching control agent, a chelating agent, a surfactant, a stabilizer, and water at 25 ℃ for 40min, and filtering the mixture through a 0.2 μm filter.
The formulations of the copper etching solutions provided in examples 1-9 are shown in Table 1:
TABLE 1 formulation composition
Comparative example 1
This comparative example provides a copper etching solution which differs from example 1 in that: the components are different.
The copper etching solution comprises the following components in percentage by mass: 5% hydrogen peroxide, 10% phosphoric acid, 2% lactic acid, 2% tartaric acid, 0.1% 5-aminotetrazole, 1.5% triethanolamine, 0.2% PE6100 and 0.5% phenylurea, the balance being water.
Specifically, the difference from example 1 is that: no second organic acid (this portion is made up with water).
Comparative example 2
This comparative example provides a copper etching solution which differs from example 1 in that: the components are different.
The copper etching solution comprises the following components in percentage by mass: 5% hydrogen peroxide, 10% phosphoric acid, 2% iminodiacetic acid, 0.1% 5-aminotetrazole, 1.5% triethanolamine, 0.2% PE6100 and 0.5% phenylurea, the balance being water.
Specifically, the difference from example 1 is that: no first organic acid (the portion is made up with water).
Comparative example 3
This comparative example provides a copper etching solution which differs from example 1 in that: the components are different.
The copper etching solution comprises the following components in percentage by mass: 5% hydrogen peroxide, 10% phosphoric acid, 2% lactic acid, 2% tartaric acid, 2% iminodiacetic acid, 1.5% triethanolamine, 0.2% PE6100 and 0.5% phenylurea, the balance being water.
Specifically, the difference from example 1 is that: no etch control agent (this portion is filled with water).
Comparative example 4
This comparative example provides a copper etching solution which differs from example 1 in that: the components are different.
The copper etching solution comprises the following components in percentage by mass: 5% hydrogen peroxide, 10% phosphoric acid, 2% lactic acid, 2% tartaric acid, 2% iminodiacetic acid, 0.1% benzotriazole, 1.5% triethanolamine, 0.2% PE6100, and 0.5% phenylurea, the balance being water.
Specifically, the difference from example 1 is that: the etching control agent is changed from 5-aminotetrazole to benzotriazole.
Comparative example 5
The copper etching solution comprises the following components in percentage by mass: 5% hydrogen peroxide, 10% phosphoric acid, 2% lactic acid, 2% tartaric acid, 2% iminodiacetic acid, 0.04% 5-aminotetrazole, 1.5% triethanolamine, 0.2% PE6100, and 0.5% phenylurea, the balance being water.
Specifically, the difference from example 1 is that: the amount of 5-aminotetrazole in the etching inhibitor is reduced from 0.1% to 0.04%, and the balance is adjusted by water correspondingly.
Comparative example 6
This comparative example provides a copper etching solution which differs from example 1 in that: the components are different.
The copper etching solution comprises the following components in percentage by mass: 5% hydrogen peroxide, 10% phosphoric acid, 2% lactic acid, 2% tartaric acid, 2% iminodiacetic acid, 0.1% 5-aminotetrazole, 0.4% triethanolamine, 0.2% PE6100 and 0.5% phenylurea, the balance being water.
Specifically, the difference from example 1 is that: the amount of triethanolamine in the chelating agent was reduced from 1.5% to 0.4%, with the balance adjusted by water.
Comparative example 7
The copper etching solution comprises the following components in percentage by mass: 5% hydrogen peroxide, 10% phosphoric acid, 2% lactic acid, 2% tartaric acid, 2% iminodiacetic acid, 0.1% 5-aminotetrazole, 1.5% triethanolamine, and 0.5% phenylurea, with the balance being water.
Specifically, the difference from example 1 is that: no surfactant is contained, and the rest amount is adjusted by water correspondingly.
Test examples
The etching points, the critical dimension loss of over-etching, the amount of dissolved copper, the etching stability and the etching uniformity of the copper etching solutions provided in examples 1 to 9 and comparative examples 1 to 7 were evaluated, and the test results are shown in the table.
The test method comprises the following steps: the exposed and developed substrate (copper thickness about 5 μm) was placed in an etching solution, the etching temperature for the experiment was set at 30 ℃ for 4min, and the various properties were tested after etching.
(1) Etching points: soaking a blank copper substrate (not subjected to glue spreading and developing) in an etching solution at 30 ℃, wherein the etching is completely an etching point;
o: 3-5min; x: <3min or >5min.
(2) Critical dimension loss for overetch: after a substrate over-etched by 50% (etching time is etching point × 1.5) was subjected to a film removal treatment, it was dried and the line width was observed using a microscope.
○：CD loss≤4μm；×：CD loss>4μm。
(3) Copper dissolution amount: copper powder with a certain concentration is added into the copper etching solution, the etching rate and the critical dimension loss of over etching are tested, and the critical point (the content of copper ions in the added etching solution before failure) is the dissolved copper amount/service life of the etching solution.
O: the amount of dissolved copper is more than 8000ppm; x: the amount of dissolved copper is less than or equal to 8000ppm.
(4) Etching uniformity COV: 20cm × 20cm of substrate to be etched is soaked in the etching solution at 30 ℃ for 4min, and the COV (coefficient of variation) of the critical dimension loss of over-etching is tested by a 16-point method after drying.
○：COV>90％；×：COV≤90％。
TABLE 2 results of performance test of etching solutions
As can be seen from the data in table 2: the copper etching solution provided by the embodiment of the application is ideal for etching 5-micron-thick copper with a line width/line distance in a node of 10 microns/10 microns, and has relatively suitable and controllable etching points, small side etching, long service life of the etching solution and uniform and excellent etching.
The copper etching solution provided by the embodiment of the application can obtain an ideal etching effect, and the dissolved copper amount can reach 9000ppm or more; when the etching solution does not contain a specific additive combination, the etching rate and the etching uniformity are not well controlled, the side etching is large, and the etching stability is poor.
In summary, the copper etching solution provided by the application is suitable for etching copper with a thickness of 4-10 μm, can obtain an etching morphology meeting requirements, can effectively control the etching rate and the loss of critical dimensions of patterns, has large etching capacity, and has a wide application prospect.
The present invention has been described in terms of the preferred embodiment, and it is not intended to be limited to the embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The copper etching solution is characterized by comprising the following components, by mass, 1-15% of inorganic acid, 4-10% of peroxide, 4-10% of organic acid and/or salt thereof, 0.5-5.0% of chelating agent, 0.05-0.5% of etching control agent, 0.1-0.5% of surfactant, 0.1-1.0% of stabilizer and the balance of water;
the organic acid comprises a first organic acid and a second organic acid; wherein the first organic acid and copper have a stability constant lg beta n of not more than 10, and the second organic acid and copper have a stability constant lg beta n of 14-20.
2. The copper etching solution according to claim 1, wherein the copper etching solution comprises 3 to 10% of an inorganic acid, 5 to 8% of a peroxide, 4 to 7% of an organic acid and/or a salt thereof, 1.5 to 3.5% of a chelating agent, 0.1 to 0.3% of an etching control agent, 0.2 to 0.4% of a surfactant, 0.3 to 0.6% of a stabilizer, and the balance being water.
3. The copper etching solution according to claim 1 or 2, wherein the first organic acid is an organic acid containing no nitrogen atom and having at least one or more carboxyl groups;
preferably, the first organic acid comprises at least one of a monocarboxylic acid and a dicarboxylic acid; wherein the monocarboxylic acid of the first organic acid comprises at least one of formic acid, butyric acid, benzoic acid, glycolic acid and lactic acid; and/or the dicarboxylic acid in the first organic acid comprises at least one of oxalic acid, malonic acid, succinic acid, tartaric acid and malic acid;
preferably, the first organic acid comprises at least one of lactic acid, oxalic acid and tartaric acid.
4. The copper etching solution according to claim 1 or 2, wherein the second organic acid is an organic acid containing a nitrogen atom;
preferably, the second organic acid includes at least one of monocarboxylic acid, dicarboxylic acid and polycarboxylic acid; wherein the monocarboxylic acid of the second organic acid comprises at least one of glutamic acid and arginine; and/or the dicarboxylic acid in the second organic acid comprises iminodiacetic acid; and/or, the polycarboxylic acid comprises at least one of nitrilotriacetic acid and ethylenediaminetetraacetic acid;
preferably, the second organic acid comprises at least one of glutamic acid, iminodiacetic acid, and ethylenediaminetetraacetic acid.
5. The copper etching liquid according to claim 1 or 2, wherein the inorganic acid is phosphoric acid; and/or the peroxide is hydrogen peroxide.
6. The copper etching liquid according to claim 1 or 2, wherein the chelating agent comprises an organic alkanolamine compound;
preferably, the chelating agent comprises at least one of monoethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine, diglycolamine, and 2-amino-2-methylpropanol;
preferably, the chelating agent is triethanolamine.
7. The copper etching solution according to claim 1 or 2, wherein the etching control agent is the one that is used for etching a copper substrateIs a tetrazole compound, and the structural formula of the tetrazole compound is as follows:
wherein R is selected from H and CH 3 And NH 3 At least one of;
preferably, the etching control agent comprises at least one of tetrazole, 5-methyl tetrazole and 5-amino tetrazole;
preferably, the etching control agent comprises at least one of 5-methyl tetrazole and 5-amino tetrazole.
8. The copper etching solution according to claim 1 or 2, wherein the surfactant is a block polyether nonionic surfactant; and/or, the stabilizer comprises at least one of phenyl urea, cyclohexylamine, 1-propanol, and ethylene glycol butyl ether;
preferably, the block polyether is a polyether containing EO-PO-EO blocks;
preferably, the molecular weight of the block polyether nonionic surfactant is 2000-5000;
preferably, the stabilizer is phenylurea.
9. The process for producing a copper etching liquid according to any one of claims 1 to 8, which comprises: the components are mixed.
10. The etching method of the glass substrate copper is characterized by comprising the following steps: etching copper on a glass substrate with the copper etching solution according to any one of claims 1 to 8;
preferably, the thickness of the copper to be etched is 4-10 μm;
preferably, the etching is carried out at 25-40 deg.C for 3-5min;
preferably, the temperature of the etching is 25-30 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211649155.9A CN115786916A (en) | 2022-12-21 | 2022-12-21 | Copper etching solution and preparation method thereof, and etching method of glass substrate copper |
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| CN202211649155.9A CN115786916A (en) | 2022-12-21 | 2022-12-21 | Copper etching solution and preparation method thereof, and etching method of glass substrate copper |
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