CN117089842A - Etching composition and application thereof - Google Patents

Etching composition and application thereof Download PDF

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Publication number
CN117089842A
CN117089842A CN202311007378.XA CN202311007378A CN117089842A CN 117089842 A CN117089842 A CN 117089842A CN 202311007378 A CN202311007378 A CN 202311007378A CN 117089842 A CN117089842 A CN 117089842A
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etching
ether
etching composition
formula
phenyl
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高小云
傅云浆
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Jingrui Electronic Materials Co ltd
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Jingrui Electronic Materials 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
    • C23F1/10—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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

The invention discloses an etching composition and application thereof, which comprises, by mass, 6.0% -15.0% of hydrogen peroxide, 70.0% -88.2% of water, 2.5% -10.0% of a compound shown in a formula (I), 0.5% -5.0% of alkyl phenyl ether and/or alkoxy phenyl ether, 2.5% -5.0% of a buffer system and 0.3% -1.0% of a chelating agent;R 1 is C 1‑6 Alkyl, phenyl or substituted phenyl, the substituents in the substituted phenyl being selected from hydroxy and/or carboxy; the buffer system is used for regulating and controlling the pH value of the etching system and does not contain fluorine, phosphorus and nitrogen, so that the change rate of the pH value of the etching system in etching is less than 1%; the etching composition has no fluorine, no phosphorus, low nitrogen content, good environmental protection, and copper content during etchingAnd the multi-layer film layer of molybdenum can keep stable etching angle, reasonable critical dimension loss and small fluctuation, ideal etching speed, no molybdenum residue and no residue.

Description

Etching composition and application thereof
Technical Field
The invention relates to the field of metal film etching liquid for flat panel display, in particular to an environment-friendly etching liquid, and specifically relates to a fluorine-free phosphorus-free low-nitrogen environment-friendly etching liquid and application thereof.
Background
In the current production process of the high-generation liquid crystal panel, the large-scale panel means that lower resistance-capacitance signal delay, shorter charging time and the like are required, so that copper and alloy materials with high conductivity and better electromigration resistance are required on wiring materials such as signal wires. Copper-containing wiring is basically produced by depositing a copper-containing multilayer film on a glass substrate, determining a desired circuit pattern using a photoresist as a mask, and etching with a wet electron chemical. The copper-containing multilayer film layer generally comprises a multilayer film of copper/molybdenum, copper/molybdenum/niobium, copper/molybdenum nitride, copper/molybdenum nitride, etc., to overcome the problem of poor adhesion between copper and glass substrate.
The current industry copper etching liquid products are mainly obtained by mixing hydrogen peroxide with acid, additives and the like, and the copper etching liquid taking hydrogen peroxide as a main body can generate a large amount of copper ions in the etching process, so that the decomposition of hydrogen peroxide and the instability of a system are greatly improved, in order to keep the stability of the etching liquid and ensure the stability of the etching liquid, a large amount of chelating agents or organic alcohol amine are usually added into the system, wherein the chelating agents comprise aminotrimethylene phosphonic acid, ethylenediamine tetramethylene phosphonic acid, hexamethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid and the like, and the organic alcohol amine comprises primary amine, secondary amine, tertiary amine and the like such as ethanolamine, diethanolamine, triethanolamine and the like, so that although a good stabilizing effect can be obtained in the etching system, the system has too high nitrogen content and is unfavorable for environmental protection;
meanwhile, the tailing phenomenon is often caused by the residual metallic molybdenum layer in the copper etching process, and the existing solution method is to solve the problem of molybdenum residue as far as possible by adding hydrofluoric acid or fluorine-containing salts such as potassium fluoride, ammonium bifluoride, sodium fluoride and the like, or by adding a large amount of organic amine such as ethanolamine, triethanolamine, dimethylethanolamine and aminomethylpropanol into a system;
in addition, the existing etching solution is basically added with corrosion inhibitors such as tetrazoles or derivatives of the same family, such as aminotetrazole, benzotriazole, thiazole and the like to inhibit the reaction rate, and the substances are generally toxic and difficult to degrade, so that the substances have destructive effects on the environment and human health.
For example, CN101684557 discloses a copper, copper molybdenum alloy electrode etching liquid in a liquid crystal display system, comprising 12 to 35% hydrogen peroxide, 0.5 to 5% phosphate, and 0.0001 to 0.5% fluoride ion, 0.1 to 5% first water-soluble cyclic amine, 0.1 to 5% second water-soluble cyclic amine, 0.1 to 5% glycol, and deionized water. The etching solution contains fluorine, is not beneficial to environmental protection and has high post-treatment pressure.
For example, CN113186531a discloses a fluorine-free etching solution, the fluorine etchant comprising, in weight percent: hydrogen peroxide in an amount of 1wt% to 25 wt%; 0.01wt% to 3wt% of an etch stabilizer; 1wt% to 20wt% of an etching inhibitor; 0.01wt% to 4wt% of a pH regulator; 1-10 wt% of auxiliary oxidant; 0.01wt% to 0.8wt% of an etching additive; and the balance of deionized water. The etching solution does not contain fluorine, but a large amount of alcohol amine and high nitrogen or phosphorus-containing compound are selected as auxiliary agents, so that the etching solution is not beneficial to environmental protection.
For example, CN112030165 discloses a copper-molybdenum alloy layer etching solution for TFT-LCD process, which comprises the following raw materials in percentage by weight: 5 to 25 percent of hydrogen peroxide, 2 to 4 percent of chelating agent, 1 to 2 percent of regulator, 0.05 to 0.5 percent of stabilizer, 0.05 to 0.5 percent of corrosion inhibitor A, 0.05 to 0.5 percent of corrosion inhibitor B, 0.5 to 1 percent of multifunctional additive and the balance of ultrapure water, wherein the chelating agent is at least one of amino trimethylene phosphonic acid, ethylenediamine tetramethylene phosphonic acid, hexamethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, dioxin triamine pentamethylene phosphonic acid and polyamino polyether methylene phosphonic acid; the regulator is phosphonobutane tricarboxylic acid; the stabilizer is phenylurea, thiourea and/or phenylacetamide; the corrosion inhibitor A is triethanolamine borate; the corrosion inhibitor B is a nitrogen-containing heterocyclic compound and is selected from at least one of imidazole, pyridine, pteridine, triamterene and 5-aminotetrazole; the multifunctional additive is tetrasodium iminodisuccinate. Although the etching solution has relatively good etching effect, the formula of the etching solution uses a large amount of substances containing nitrogen and phosphorus, which is not beneficial to environmental protection.
The copper etching solution has huge consumption, and the existing etching solution basically contains more structural components such as phosphorus, fluorine, nitrogen and the like, so that the treatment of waste liquid after etching brings great challenges. Along with the stricter national environmental protection policy, panel display factories propose the requirements of fluorine-free, phosphorus-free and low nitrogen of etching solutions.
Disclosure of Invention
The present invention aims to overcome one or more of the disadvantages of the prior art and to provide an improved etching composition which is capable of maintaining stable etching angles, reasonable critical dimension loss and small fluctuations, ideal etching rate, no molybdenum residue, no residue on an environmentally friendly basis of fluorine-free, phosphorus-free, low nitrogen.
The invention also provides application of the etching composition in etching copper-and molybdenum-containing multilayer film layers, including but not limited to copper/molybdenum, copper/molybdenum/niobium, copper/molybdenum nitride, copper/molybdenum nitride and other multilayer film layers.
In order to achieve the above purpose, the invention adopts a technical scheme that:
an etching composition comprising a) hydrogen peroxide, b) water, c) a compound of formula (i) having the formula:
R 1 is C 1-6 An alkyl group, a phenyl group or a substituted phenyl group, the substituents in the substituted phenyl group being selected from hydroxy and/or carboxy;
d) Alkyl phenyl ethers and/or alkoxy phenyl ethers;
e) The buffer system is used for regulating and controlling the pH value of the etching system and does not contain fluorine, phosphorus and nitrogen, so that the change rate of the pH value of the etching system in etching is less than 1%;
f) A chelating agent;
in mass percent, the etching composition comprises a) 6.0% -15.0% of hydrogen peroxide, b) 70.0% -88.2% of water, c) 2.5% -10.0% of a compound shown as a formula (I), d) 0.5% -5.0% of alkyl phenyl ether and/or alkoxy phenyl ether, e) 2.5% -5.0% of a buffer system and f) 0.3% -1.0% of a chelating agent.
Further, in the etching composition, a) hydrogen peroxide accounts for 6.0 to 12.0% by mass.
Further, the compound represented by the formula (I) of c) accounts for 2.5 to 8.0% by mass of the etching composition. In some embodiments, the compound of formula (i) comprises 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, etc., by mass percent of the etching composition.
Further, in the etching composition, d) alkyl phenyl ether and/or alkoxy phenyl ether accounts for 0.5% -4.0% by mass. In some embodiments, d) alkyl phenyl ether and/or alkoxy phenyl ether comprises 0.5%, 0.8%, 1.0%, 1.2%, 1.5%, 1.8%, 2.0%, 2.5%, 3.0%, 3.5%, etc., by mass percent in the etching composition.
Further, in the etching composition, e) the buffer system accounts for 2.5% -4.5% by mass. In some embodiments, the e) buffer system comprises 2.6%, 2.8%, 3.0%, 3.2%, 3.6%, 3.8%, 4.0%, 4.2%, etc., by mass percent of the etching composition.
In some embodiments of the invention, component b) is pure water.
In some embodiments of the present invention, hydrogen peroxide may be added by adding an aqueous hydrogen peroxide solution, which may be 30% -50%, etc., and when added as an aqueous hydrogen peroxide solution, the amount of hydrogen peroxide may be calculated according to the formulation to add an appropriate mass of aqueous hydrogen peroxide solution.
According to some preferred aspects of the invention, R 1 Is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, phenyl, hydroxyphenyl (for example, it may be) Carboxyphenyl (for example, & lt + & gt>) Or salicylic acid group->
In some embodiments of the present invention, the compound of formula (I) may be selected from the group consisting of phenolsulfonic acid (including ortho-phenolsulfonic acid, meta-phenolsulfonic acid, para-phenolsulfonic acid), methylsulfonic acid, 5-sulfosalicylic acid, and the like.
According to some preferred aspects of the present invention, the alkyl phenyl ether is selected from compounds of formula (II), wherein the compounds of formula (II) have the formula:
R 2 is C 1-6 Alkoxy or hydroxy substituted C 1-6 Alkoxy, t is 1, 2, 3 or 4.
In some embodiments of the invention, R 2 Methoxy, ethoxy, propoxy, isopropoxy, hydroxy-substituted methoxy, hydroxy-substituted ethoxy, hydroxy-substituted propoxy, hydroxy-substituted isopropoxy, and the like.
According to some preferred aspects of the present invention, the alkoxyphenyl ether is selected from compounds of formula (iii), wherein the compounds of formula (iii) have the formula:
R 3 is C 1-6 Alkylene group, R 4 Is C 1-6 Alkyl-or hydroxy-substituted C 1-6 An alkyl group.
In some embodiments of the invention, R 3 Is methylene, ethylene, propylene, isopropylene, etc., R 4 Is methyl, ethyl, propyl, isopropyl, hydroxy-substituted methyl, hydroxy-substituted ethyl, hydroxy-substituted propyl, hydroxy-substituted isopropyl, or the like.
According to some preferred and specific aspects of the present invention, component d) is selected from one or more combinations of phthalic ether, phthalic diethyl ether, phthalic dipropyl ether, 2-hydroxy phenyl propyl ether, 2-hydroxy phenyl ethyl ether, 2-hydroxy phenyl methyl ether, 3-hydroxy phenyl propyl ether, 3-hydroxy phenyl ethyl ether, p-hydroxy phenyl propyl ether, p-hydroxy phenyl ethyl ether, p-hydroxy phenyl methyl ether, diethylene glycol monophenyl ether, ethoxy phenyl ether and propoxy phenyl ether.
According to some preferred and specific aspects of the invention, the buffer system is used to regulate the pH of the etching system to always be 2.5-3.5.
According to the invention, the etching composition is free of fluorine and phosphorus.
According to some preferred aspects of the invention, the buffer system consists of acetic acid and a water-soluble acetate salt, the molar ratio of acetic acid to acetate salt being in the range of 1:0.25 to 1.35.
Further, the acetate is sodium acetate and/or potassium acetate.
In some embodiments of the invention, the buffer system is comprised of acetic acid and potassium acetate, the acetic acid to potassium acetate feed mass ratio is 7:3 to 7:15.
In some embodiments of the invention, the chelating agent is a combination of one or more selected from iminodiacetic acid, nitrilotriacetic acid, tetraacetic acid oxalate, tetrahydroxypropylethylenediamine, and glycine.
The invention provides another technical scheme that: a method of preparing the etching composition described above, the method comprising: and uniformly mixing the components in the etching composition.
In some embodiments of the present invention, the mixing may be performed by stirring or shaking, etc.
In some embodiments of the present invention, hydrogen peroxide is added in the form of an aqueous hydrogen peroxide solution (hydrogen peroxide), and the method of preparing the etching composition includes: and mixing the components except the hydrogen peroxide water solution in the formula, dispersing and dissolving, stirring uniformly, adding the hydrogen peroxide water solution, and mixing uniformly to prepare the aqueous hydrogen peroxide.
The invention provides another technical scheme that: use of an etching composition as described above for etching a copper and molybdenum containing multilayer film.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, by constructing a new formula system, the components exert synergistic effect, the balance of the system is utilized to adjust, corrosion inhibitors harmful to human bodies such as azoles and derivatives thereof are not needed to control the etching rate, the etching angle is kept at 40-55 ℃ in the etching period of 0-6000 ppm of copper ions, the fluctuation is small, the single-side CD loss is controlled at 0.75-0.85 microns, the stability is good, molybdenum residues and residues are avoided.
In addition, the etching composition disclosed by the invention is fluorine-free, phosphorus-free, low in nitrogen and good in environmental friendliness, and reduces the wastewater treatment pressure.
Drawings
FIG. 1 is a cross-sectional view of a glass substrate etched at 0ppm of copper ions in the etching composition prepared in example 1 of the present invention;
FIG. 2 is a cross-sectional view of a glass substrate etched at 2000ppm of copper ions in the etching composition prepared in example 1 of the present invention;
FIG. 3 is a cross-sectional view of a glass substrate etched at 4000ppm of copper ions in the etching composition prepared in example 1 of the present invention;
FIG. 4 is a sectional view of a glass substrate scanning electron microscope etched at 6000ppm of copper ions in the etching composition prepared in example 1 of the present invention.
Detailed Description
The main conception of the invention is that: through the integral conception and construction of the formula, the components are mutually influenced in the system to realize the synergistic effect, and a single component realizes multiple functions; the compound shown in the formula (I) and hydrogen peroxide are linked to enable the copper-and molybdenum-containing multilayer film to be corroded, participate in the reaction with copper oxide, assist in complexing part of copper ions generated, and be beneficial to etching the molybdenum layer and preventing molybdenum tail from forming; the alkyl phenyl ether and/or the alkoxy phenyl ether are added into the system, so that the hydrogen peroxide can be restrained from being excessively activated to accelerate the decomposition, meanwhile, the effect of complexing part copper ions can be born, the viscosity of the system can be regulated, and the stability of the etching rate in the etching period can be cooperatively controlled; the pH value of the etching system is regulated and controlled by combining a buffering agent system without fluorine, phosphorus and nitrogen, so that the stability of the etching system is ensured, and meanwhile, the dosage of the chelating agent can be obviously reduced by the action of the synergetic complexing copper ions of a plurality of components in the formula, so that the concentration of nitrogen atoms in the system can be greatly reduced; in addition, the whole etching system realizes self balance adjustment through the combination of the components, and corrosion inhibitors harmful to human bodies such as azoles, derivatives thereof and the like are not needed to control the etching rate.
Based on the above concepts, the present invention provides an etching composition comprising a) hydrogen peroxide, b) water, c) a compound of formula (i) having the structural formula:R 1 is C 1-6 An alkyl group, a phenyl group or a substituted phenyl group, the substituents in the substituted phenyl group being selected from hydroxy and/or carboxy; d) Alkyl phenyl ethers and/or alkoxy phenyl ethers; e) The buffer system is used for regulating and controlling the pH value of the etching system and does not contain fluorine, phosphorus and nitrogen, so that the change rate of the pH value of the etching system in etching is less than 1%; f) Chelating agents.
Further, in the system of the present invention, the mass percentage of the hydrogen peroxide of the component a) is preferably 6.0% -15.0%, and the practice shows that if the content is less than 6%, the metal oxide capability is insufficient, the etching rate is low, but if the content of the hydrogen peroxide is more than 15%, the copper ions are obviously increased, so that the hydrogen peroxide is subjected to linkage decomposition, and the system is unstable.
Further, in the system of the present invention, the mass percentage of the compound represented by the formula (I) of the component c) is preferably 2.5% to 10.0%, and if the content is less than 2.5%, the etching rate may be affected, the reaction is slow, and molybdenum residue is obvious; if the content is too high, on one hand, the reaction rate is faster, the unilateral CD loss is not easy to control, and on the other hand, the pH value is lower, which is unfavorable for complexing copper ions.
Further, in the system of the present invention, the content of the component d) alkyl phenyl ether and/or alkoxy phenyl ether is preferably 0.5% to 5.0% by mass, and if the content is too low, the decomposition rate of hydrogen peroxide is increased, so that the system is at risk of bumping, and the solubility of the components in the system is limited, and the etching solution is not dissolved in too high content, so that the system is easily unstable.
Further, in the system of the present invention, the content of the buffer system of component e) is preferably 2.5% to 5.0% by mass, and if the content is too low, the pH is liable to be unstable at the end of etching, the pH change rate will be higher than 5%, the fluctuation of etching rate becomes large, and if the content of the buffer system is too high, the cost is increased, which is not necessary. Preferably, under the system of the invention, acetic acid and acetate such as potassium acetate system which do not contain fluorine, phosphorus and nitrogen are preferably selected, and the feeding mole ratio of the acetic acid and the acetate is preferably controlled to be 1:0.25-1.35 (when the acetate is potassium acetate, the weight ratio is controlled to be 7:3-7:15), the total content is about 2.5% -5%, the pH value of the acetic acid and the potassium acetate stable system is about 2.5-3.5, for example about 3, even if a large amount of copper ions are dissolved into the etching system at the end of etching, the whole pH value change rate is lower than 1%, the stability of the system from beginning to end is ensured, and the raw materials with high nitrogen content such as primary amine, secondary amine, tertiary amine and the like are avoided from being added into the conventional etching system.
Furthermore, in the system of the invention, the chelating agent mainly plays a role of complexing copper ions, so that on one hand, the decomposition of hydrogen peroxide is reduced, and on the other hand, the generation of etching residues in the solution caused by excessive copper ions is prevented. According to the invention, through the integral linkage of the components, the dosage of the chelating agent is obviously reduced, the concentration of nitrogen atoms is greatly reduced, the content of the nitrogen atoms is controlled within 1200ppm, and the wastewater treatment pressure is further reduced. The content of the chelating agent can be controlled to be 0.3% -1%, the chelating agent is too low, copper ion complexation is not facilitated, etching residues possibly appear, the chelating agent is too high, the system is not changed, and unnecessary waste is caused.
The above-described aspects are further described below in conjunction with specific embodiments; it should be understood that these embodiments are provided to illustrate the basic principles, main features and advantages of the present invention, and that the present invention is not limited by the scope of the following embodiments; the implementation conditions employed in the examples may be further adjusted according to specific requirements, and the implementation conditions not specified are generally those in routine experiments.
The purity of the component raw materials used in the following examples and comparative examples are analytically pure and above grade purity, and all raw materials may be obtained from commercial sources or prepared by a conventional method in the art, unless otherwise specified.
Example 1
The example provides an etching composition and a preparation method thereof, wherein the etching composition comprises 8% of hydrogen peroxide, 3% of o-phenolsulfonic acid, 1% of o-phthalether, 3.5% of a buffer system, 0.5% of iminodiacetic acid and the balance of water in percentage by mass; wherein the buffer system consists of acetic acid and potassium acetate, the mass ratio of the acetic acid to the potassium acetate is 7:10, and hydrogen peroxide is added in the form of 30% hydrogen peroxide aqueous solution (hydrogen peroxide).
The preparation method of the etching composition comprises the following steps: and mixing the components except the hydrogen peroxide water solution in the formula, dispersing and dissolving, stirring uniformly, adding the hydrogen peroxide water solution, and mixing uniformly to prepare the aqueous hydrogen peroxide.
Example 2
Substantially the same as in example 1, the only difference is that: iminodiacetic acid is replaced with nitrilotriacetic acid of equivalent added mass.
Example 3
Substantially the same as in example 1, the only difference is that: o-phenolsulfonic acid was replaced with methylsulfonic acid of equivalent added mass.
Example 4
Substantially the same as in example 1, the only difference is that: the o-phenolsulfonic acid is replaced by 5-sulfosalicylic acid with the same added mass.
Example 5
Substantially the same as in example 3, the only difference is that: the mass ratio of acetic acid to potassium acetate is 7:13.
Example 6
Substantially the same as in example 1, the only difference is that: the amount of buffer system was adjusted to 4.5% with a corresponding decrease in the amount of water added.
Example 7
Substantially the same as in example 1, the only difference is that: o-phenolsulfonic acid was replaced with ethyl sulfonic acid of equivalent added mass.
Example 8
Substantially the same as in example 1, the only difference is that: the o-phthaloyl ether is replaced by 2-hydroxy phenylpropyl ether with the same added mass.
Example 9
Substantially the same as in example 1, the only difference is that: the o-phthalmether is replaced by diethylene glycol monophenyl ether with the same added mass.
Example 10
Substantially the same as in example 1, the only difference is that: the o-phthalmether is replaced by the propoxyphenyl ether with the same added mass.
Example 11
Substantially the same as in example 1, the only difference is that: the o-phthalmether is replaced by ethoxyphenyl ether with the same added mass.
Example 12
Substantially the same as in example 1, the only difference is that: the addition amount of hydrogen peroxide was adjusted to 10%, and the addition amount of water was correspondingly reduced.
Example 13
Substantially the same as in example 1, the only difference is that: the addition amount of the o-phenolsulfonic acid is adjusted to 5%, and the addition amount of water is correspondingly reduced.
Example 14
Substantially the same as in example 1, the only difference is that: the addition amount of the o-phthaloyl ether is adjusted to 2 percent, and the addition amount of water is correspondingly reduced.
Comparative example 1
Substantially the same as in example 1, the only difference is that: the o-phenolsulfonic acid is replaced by citric acid with the same addition.
Comparative example 2
Substantially the same as in example 1, the only difference is that: the o-phenolsulfonic acid was replaced with 98% sulfuric acid.
Comparative example 3
Substantially the same as in example 1, the only difference is that: the o-phthaloyl ether is replaced by polyethylene glycol with the same addition amount.
Comparative example 4
Substantially the same as in example 1, the only difference is that: the iminodiacetic acid content was reduced to 0.1%, and the water addition was increased accordingly.
Comparative example 5
Substantially the same as in example 1, the only difference is that: the content of the o-phenol sulfonic acid is reduced to 1 percent, and the addition amount of water is correspondingly increased.
Comparative example 6
Substantially the same as in example 1, the only difference is that: the content of the buffer system was reduced to 1.5%, and the amount of water added was increased accordingly.
Comparative example 7
Substantially the same as in example 1, the only difference is that: the mass ratio of acetic acid to potassium acetate is 7:20.
Comparative example 8
Substantially the same as in example 1, the only difference is that: the mass ratio of acetic acid to potassium acetate is 7:1.
Comparative example 9
Substantially the same as in example 1, the only difference is that: the addition amount of the o-phthaloyl ether is reduced to 0, and the addition amount of water is correspondingly increased.
Comparative example 10
Substantially the same as in example 1, the only difference is that: the addition amount of the o-phthaloyl ether is reduced to 0.1 percent, and the addition amount of water is correspondingly increased.
Performance testing
Preparing a substrate: sequentially depositing on a glass substrate a thickness ofMolybdenum layer->And forming a copper layer, forming a copper-molybdenum double-layer film, coating a photoresist on the deposited film layer, performing exposure and development to form a photomask, and etching the copper-molybdenum double-layer film which is not covered by the photomask by using the etching compositions prepared in the above examples 1 to 14 and comparative examples 1 to 10.
Etching experiment: 1L each of the etching compositions prepared in examples 1 to 14 and comparative examples 1 to 10 was added to a beaker, the temperature was kept at 30℃and the stirring speed was set at 250r/min, the substrate was cut into 10cm by 10cm, and immersed in the liquid medicine, and the etching time was set at 120s. And (5) washing with pure water and air-drying immediately after etching. The cross-sectional shape of the substrate, etching angle, CD loss, molybdenum residue and residue were confirmed by a scanning electron microscope (model: hitachi S4800). The residual ratio of hydrogen peroxide before and after the reaction is detected by an acid-base titration method, and the hydrogen peroxide decomposition rate (new hydrogen peroxide content-old hydrogen peroxide content)/new hydrogen peroxide content is calculated to be 100%.
The etching action was repeated every 2000ppm,4000ppm,6000ppm to test glass substrates at a rate of 1000ppm copper powder per hour to the etching compositions prepared in examples 1-14 and comparative examples 1-10 described above to simulate a production line.
The sectional view of a glass substrate etched at 0ppm,2000ppm,4000ppm,6000ppm of copper ions in the etching composition prepared in example 1 is shown in FIGS. 1 to 4.
Evaluation results
The results of etching in etching of the etching compositions prepared in examples 1 to 14 and comparative examples 1 to 10 are shown in tables 1 and 2.
TABLE 1
TABLE 2
Comparative example 1 the phenolsulfonic acid was replaced with citric acid of the same addition amount, and under this etching system, the copper ion chelating ability was insufficient in the middle and later stages of etching, the hydrogen peroxide decomposition rate was remarkably increased, the CD loss was decreased, the etching angle was increased, and molybdenum residues and etching residues were present.
Comparative example 2 the phenolsulfonic acid was replaced with 98% sulfuric acid of the same concentration, and the etching rate was too high in this etching system, and molybdenum residue and etching residues were generated from the beginning, and the hydrogen peroxide decomposition rate was too high at the end.
In comparative example 3, the o-phthaloyl ether was replaced with polyethylene glycol of the same addition amount, the etching angle and CD loss fluctuation were large, the end-stage hydrogen peroxide decomposition rate was high, and molybdenum residue and etching residues appeared.
Comparative example 4 the chelating agent IDA content was 0.1%, the copper ion chelating ability was insufficient in the middle and later stages of etching, the hydrogen peroxide decomposition rate was remarkably accelerated, the etching rate was decreased, the CD loss was decreased, the etching angle was increased, and molybdenum residues and etching residues were present.
Comparative example 5 ortho-phenolsulfonic acid content was 1%, the etching solution acidity was insufficient, and CD loss and etching angle fluctuation were large in the whole etching period.
Comparative examples 6,7 and 8 are all solutions of insufficient acetic acid and potassium acetate or mismatched buffer ratios, and unstable pH values during the whole etching period, resulting in increased hydrogen peroxide decomposition rate, large CD loss and etching angle fluctuation, and molybdenum residues and residues.
In comparative examples 9 and 10, after the stabilizer phthalic ether was not added or the content was 0.1%, hydrogen peroxide could not be effectively inhibited after being activated, hydrogen peroxide was decomposed drastically, fluctuation of CD loss and etching angle was large, and the system was out of control.
As can be seen from the results of the comparative examples and the examples, the copper-molybdenum etching solution system not only avoids using phosphorus-containing and fluorine-containing raw materials and greatly reduces the investment of nitrogen-containing raw materials, but also has comprehensive coordination effect of all the components, and the defect of etching data can be caused by the lack or the mismatching of the content of any component.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

Claims (10)

1. An etching composition comprising a) hydrogen peroxide, b) water, characterized in that the etching composition further comprises:
c) A compound of formula (i) having the formula:
R 1 is C 1-6 An alkyl group, a phenyl group or a substituted phenyl group, the substituents in the substituted phenyl group being selected from hydroxy and/or carboxy;
d) Alkyl phenyl ethers and/or alkoxy phenyl ethers;
e) The buffer system is used for regulating and controlling the pH value of the etching system and does not contain fluorine, phosphorus and nitrogen, so that the change rate of the pH value of the etching system in etching is less than 1%;
f) A chelating agent;
in mass percent, the etching composition comprises a) 6.0% -15.0% of hydrogen peroxide, b) 70.0% -88.2% of water, c) 2.5% -10.0% of a compound shown as a formula (I), d) 0.5% -5.0% of alkyl phenyl ether and/or alkoxy phenyl ether, e) 2.5% -5.0% of a buffer system and f) 0.3% -1.0% of a chelating agent.
2. The etching composition of claim 1, wherein R 1 Is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, phenyl, hydroxyphenyl, carboxyphenyl or salicyl.
3. The etching composition according to claim 1, wherein the alkyl phenyl ether is selected from the group consisting of compounds of formula (ii), wherein the compounds of formula (ii) have the structural formula:
R 2 is C 1-6 Alkoxy or hydroxy substituted C 1-6 Alkoxy, t is 1, 2, 3 or 4.
4. The etching composition of claim 1, wherein the alkoxyphenyl ether is selected from the group consisting of compounds of formula (iii), wherein the compound of formula (iii) has the formula:
R 3 is C 1-6 Alkylene group, R 4 Is C 1-6 Alkyl-or hydroxy-substituted C 1-6 An alkyl group.
5. The etching composition of claim 1, 3 or 4, wherein component d) is selected from one or more of the group consisting of phthalether, phthalpropyl ether, 2-hydroxyphenylpropyl ether, 2-hydroxyphenylethyl ether, 2-hydroxyphenylmethyl ether, 3-hydroxyphenylpropyl ether, 3-hydroxyphenylethyl ether, 3-hydroxyphenylmethyl ether, p-hydroxyphenylpropyl ether, p-hydroxyphenylethyl ether, p-hydroxyphenylmethyl ether, diethylene glycol monophenyl ether, ethoxyphenyl ether, and propoxyphenyl ether.
6. The etching composition according to claim 1, wherein the buffer system is used for regulating the pH of the etching system to be always 2.5-3.5; and/or the etching composition is free of fluorine and phosphorus.
7. The etching composition according to claim 1 or 6, wherein the buffer system is composed of acetic acid and acetate which is soluble in water, and the molar ratio of acetic acid to acetate is 1:0.25-1.35.
8. Etching composition according to claim 7, characterized in that the acetate is sodium acetate and/or potassium acetate.
9. The etching composition of claim 1 wherein the chelating agent is a combination of one or more selected from iminodiacetic acid, nitrilotriacetic acid, oxalic acid tetraacetic acid, tetrahydroxypropylethylenediamine, and glycine.
10. Use of an etching composition according to any one of claims 1 to 9 for etching a multilayer film layer comprising copper and molybdenum.
CN202311007378.XA 2023-08-11 2023-08-11 Etching composition and application thereof Pending CN117089842A (en)

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