CN118957588B - Metal film wiring etching solution and preparation method and application thereof - Google Patents
Metal film wiring etching solution and preparation method and application thereof Download PDFInfo
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- 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
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Abstract
本发明公开了金属膜配线蚀刻液、金属膜配线的刻蚀方法及应用，涉及蚀刻液技术领域。以氧化性铈盐、有机磺酸、过氧类化合物、安定剂、功能化离子液体、氨基酸基低聚物、焦硫酸盐、醇醚类溶剂、Gemini表面活性剂和水为原料，各原料之间协同配合，过氧类化合物能够将蚀刻液中的还原态的Ce(III)离子进一步氧化还回成Ce(IV)离子，实现Ce(IV)离子的循环使用，通过协同醇醚类溶剂和氨基酸基低聚物以实现蚀刻液的长效寿命。制得的蚀刻液能够在不发生光刻胶抗蚀刻层渗透的前提下高效蚀刻铬金属膜配线结构，改善了现有的蚀刻液往往仅能满足某一种金属膜配线结构的蚀刻技术问题，可有效应用于不同规格铬及铬复合膜制程配线的蚀刻。The invention discloses a metal film wiring etching liquid, an etching method for metal film wiring and an application thereof, and relates to the technical field of etching liquid. Oxidizing cerium salt, organic sulfonic acid, peroxide compound, stabilizer, functionalized ionic liquid, amino acid oligomer, pyrosulfate, alcohol ether solvent, Gemini surfactant and water are used as raw materials, and the raw materials cooperate with each other. The peroxide compound can further oxidize the reduced Ce(III) ions in the etching liquid back to Ce(IV) ions, so as to realize the recycling of Ce(IV) ions, and the long-term service life of the etching liquid is realized by cooperating with alcohol ether solvent and amino acid oligomer. The prepared etching liquid can efficiently etch the chromium metal film wiring structure without the penetration of the photoresist anti-etching layer, which improves the etching technical problem that the existing etching liquid can only meet the etching of a certain metal film wiring structure, and can be effectively applied to the etching of chromium and chromium composite film process wiring of different specifications.
Description
Technical Field
The invention relates to the technical field of etching solutions, in particular to a metal film wiring etching solution, a preparation method and application thereof.
Background
Chromium metal has abundant reserves in nature, low price, and is widely used as electrode materials, wiring materials and mask masking materials in the manufacture of thin film transistor liquid crystal displays (TFT-LCD) and organic light emitting diode displays (OLED) due to the characteristics of corrosion resistance, oxidation resistance, high thermal stability, excellent electrical conductivity, good light shielding property, excellent adhesiveness with other metals and glass substrates and the like.
With the continuous upgrade of OLED and TTF-LCD device manufacturing technologies, the development demands of high definition and large size are presented, and stricter requirements are put forward on the fineness of etching and the performance requirements of etching solution, while the performance of the existing chromium etching solution is difficult to meet the requirements, and the defects are mainly presented:
(1) The components of the etching solution are changed in the etching process, so that the service life of the etching solution is seriously influenced;
(2) The problem of uneven etching rate is easy to occur, the side etching amount is easy to be large, and the line width precision after etching is affected;
(3) In the etching process, etching liquid is easy to permeate to induce undercutting, so that the surface roughness of the area without etching the chromium metal film is increased;
(4) The conventional etching solution can only meet the etching requirement of a certain metal film wiring structure, and has poor universality.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a metal film wiring etching solution and a preparation method thereof, which aims to prolong the service life of the etching solution, improve the etching precision and ensure that the etched surface is smooth and has no residue.
Another object of the present invention is to provide a method for etching a metal film wiring, which aims to improve etching accuracy and to make the etched surface smooth and free from residues.
Another object of the present invention is to provide an application of the metal film wiring etchant as an electrode material, a wiring material or rework in the manufacture of a thin film transistor liquid crystal display or an organic light emitting diode display.
The invention is realized in the following way:
in the first aspect, the invention provides a metal film wiring etching solution, which comprises 8-25% of cerium oxide salt, 0.5-9.5% of organic sulfonic acid, 2-13% of peroxy compound, 0.5-3.5% of stabilizer, 0.02-1.0% of functionalized ionic liquid, 0.2-2.5% of amino acid-based oligomer, 0.5-3.5% of pyrosulfate, 0.8-5.5% of alcohol ether solvent, 0.05-2.5% of Gemini surfactant and the balance of water.
In an alternative embodiment, the organic acid-free water-soluble cerium oxide powder comprises, by mass, 12% -23% of cerium oxide salt, 2% -8% of organic sulfonic acid, 3.5% -11% of peroxy compound, 0.8% -2.5% of stabilizer, 0.1% -0.85% of functionalized ionic liquid, 0.5% -2.0% of amino acid-based oligomer, 0.85% -2.5% of pyrosulfate, 1% -4.5% of alcohol ether solvent, 0.1% -1.5% of Gemini surfactant and the balance of water.
In an alternative embodiment, the cerium oxide salt is selected from at least one of ammonium cerium nitrate, sodium cerium nitrate, potassium cerium nitrate, ammonium cerium sulfate, sodium cerium sulfate, and potassium cerium sulfate;
preferably, the organic sulfonic acid is selected from at least one of sulfamic acid, hydroxylamine sulfonic acid, isethionic acid and 3-hydroxy propane sulfonic acid;
preferably, the peroxygen compound is selected from at least one of urea peroxide, peracetic acid, sodium peroxide and sodium peroxycarbonate.
In an alternative embodiment, the stabilizer is selected from at least one of polyethylene glycol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, and 1, 10-decanediol.
In an alternative embodiment, the functionalized ionic liquid is selected from at least one of an amino-containing functionalized ionic liquid and a hydroxyl-containing functionalized ionic liquid;
Preferably, the amino-containing functionalized ionic liquid is selected from at least one of 1-aminoethyl-3-methylimidazole nitrate, 1-aminoethyl-3-methylimidazole tetrafluoroborate, 1-aminoethyl-3-methylimidazole hexafluorophosphate, 1-aminoethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1-aminopropyl-3-methylimidazole nitrate, 1-aminopropyl-3-methylimidazole tetrafluoroborate, and 1-aminopropyl-3-methylimidazole hexafluorophosphate;
Preferably, the hydroxyl-containing functionalized ionic liquid is selected from at least one of 1-hydroxyethyl-3-methylimidazole tetrafluoroborate, 1-hydroxyethyl-3-methylimidazole hexafluorophosphate, 1-hydroxyethyl-3-methylimidazole acetate, 1-hydroxyethyl-3-methylimidazole p-toluenesulfonate, 1-hydroxyethyl-3-methylimidazole bisulfate, 1-hydroxyethyl-3-methylimidazole dihydrogen phosphate, 1-hydroxyethyl-2, 3-dimethylimidazole tetrafluoroborate and 1-hydroxyethyl-2, 3-dimethylimidazole hexafluorophosphate.
In an alternative embodiment, the amino acid based oligomer is a copolymer of an amino acid and an organic acid and has a number average molecular weight of 1500 to 4500;
Preferably, the amino acid based oligomer is selected from at least one of aspartic acid-citric acid copolymer, serine-citric acid copolymer, lysine-citric acid copolymer, cysteine-citric acid copolymer, aspartic acid-malic acid copolymer, serine-malic acid copolymer, lysine-malic acid copolymer, and cysteine-malic acid copolymer.
The amino acid base oligomer is prepared from amino acid, binary organic acid malic acid and ternary organic acid citric acid through amidation reaction, and the reaction principle is as follows:
Specifically, taking the synthesis of an aspartic acid-citric acid copolymer as an example, an amino group in aspartic acid and a carboxyl group in citric acid undergo an amidation reaction to obtain the aspartic acid-citric acid copolymer. The specific synthesis process comprises the steps of heating and polymerizing diammonium phosphate and N, N-dimethylformamide serving as catalysts (the molar ratio of the catalyst to the total amount of monomers is 8.5:100) and solvents in a microwave oven with the power of 1000w for 7-12 minutes to obtain an intermediate product (formula A), dissolving the cooled intermediate product by using a 4mol/L tetramethylammonium hydroxide solution, filtering, further regulating the pH value of a supernatant to 3.8-4.4 by using hydrochloric acid, precipitating and separating by using excessive absolute ethyl alcohol, and drying the precipitate in a 75 ℃ drying oven for 12 hours to obtain the aspartic acid-citric acid copolymer (formula B).
In an alternative embodiment, the pyrosulfates are each selected from at least one of sodium pyrosulfate, ammonium pyrosulfate, and potassium pyrosulfate;
Preferably, the alcohol ether solvents are at least one selected from ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether and triethylene glycol butyl ether;
preferably, the Gemini surfactant is selected from at least one of Surfynol420, surfynol440, surfynol465 and Surfynol 485.
According to the second aspect, the invention also provides a preparation method of the metal film wiring etching solution in any of the above embodiments, comprising the steps of mixing cerium oxide salt, organic sulfonic acid, peroxy compound, stabilizer, functional ionic liquid, amino acid-based oligomer, pyrosulfate, alcohol ether solvent, gemini surfactant and water according to the composition and the proportion of the metal film wiring etching solution;
Preferably, the mixing temperature is controlled to be 20-40 ℃, the stirring rotation speed is 80-200 r/min, and the stirring time is 1-2.5 h.
In a third aspect, the present invention also provides a method for etching a metal film wiring, including etching a glass substrate on which a metal film is deposited using the metal film wiring etching solution in any of the above embodiments;
Preferably, the glass substrate deposited with the metal film is immersed in the metal film wiring etching solution for etching, the etching temperature is controlled to be 25-55 ℃, and the etching time is controlled to be 50-175 sec;
Preferably, the metal film is a chromium or chromium-based composite film, and the thickness of the metal film is 800A-7500A.
In a fourth aspect, the present invention also provides a metal film wiring etching solution in any of the above embodiments for electrode material wiring etching, wiring material wiring etching, or film-removing reworking in the manufacture of a thin film transistor liquid crystal display or an organic light emitting diode display.
The invention has the following beneficial effects that the cerium oxide, organic sulfonic acid, peroxy compound, stabilizer, functionalized ionic liquid, amino acid base oligomer, pyrosulfate, alcohol ether solvent, gemini surfactant and water are taken as raw materials, the dosage of each component is adjusted, the raw materials are matched in a synergistic way, the peroxy compound can further oxidize the reduced Ce (III) ions in the etching solution back into Ce (IV) ions, the recycling of the Ce (IV) ions is realized, and the long-acting life of the etching solution is further realized by the synergistic way of the alcohol ether solvent and the amino acid base oligomer. The etching solution prepared by the invention can efficiently etch the chromium metal film wiring structure on the premise of not generating penetration of the photoresist etching-resistant layer, improves the technical problem that the existing etching solution can only meet the etching of a certain metal film wiring structure, and can be effectively applied to etching of wirings of chromium and chromium composite film processes with different specifications. The etching solution prepared by the invention can regulate and control the etching rate, etching contour and pattern fineness of the etching solution on metal films with different specifications, and finally, the etching effects of low line width loss, good etching taper angle, no metal residue and smooth plane are obtained.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The embodiment of the invention provides a metal film wiring etching solution, which comprises, by mass, 8% -25% of cerium oxide salt, 0.5% -9.5% of organic sulfonic acid, 2% -13% of peroxy compounds, 0.5% -3.5% of stabilizers, 0.02% -1.0% of functionalized ionic liquids, 0.2% -2.5% of amino acid-based oligomers, 0.5% -3.5% of pyrosulfate, 0.8% -5.5% of alcohol ether solvents, 0.05% -2.5% of Gemini surfactants and the balance of water.
The invention takes cerium oxide salt, organic sulfonic acid, peroxy compound, stabilizer, functional ionic liquid, amino acid base oligomer, pyrosulfate, alcohol ether solvent, gemini surfactant and water as raw materials, and adjusts the dosage of each component, so that the prepared etching solution can regulate and control the etching rate, etching contour and pattern fineness of the etching solution on metal films with different specifications, and finally, the etching effects of low line width loss, good etching taper angle, no metal residue and smooth plane are obtained. The use amount of each component is preferably in the above range, and if the use amount exceeds the above range, adverse effects are generated on etching accuracy and service life, and problems of unsmooth surface morphology and residual after etching are easy to occur.
In a preferred embodiment, the organic acid-free water-based paint comprises, by mass, 12% -23% of cerium oxide salt, 2% -8% of organic sulfonic acid, 3.5% -11% of peroxy compound, 0.8% -2.5% of stabilizer, 0.1% -0.85% of functionalized ionic liquid, 0.5% -2.0% of amino acid-based oligomer, 0.85% -2.5% of pyrosulfate, 1% -4.5% of alcohol ether solvent, 0.1% -1.5% of Gemini surfactant and the balance of water. The etching precision can be further improved and the service life can be prolonged by optimizing the use amount of each component.
The cerium oxide salt mainly plays a role in oxidizing the chromium metal film in an acidic environment, the mass fraction of the cerium oxide salt is controlled to be 8% -25%, when the mass fraction of the cerium oxide salt is lower than 8%, the etching rate of the chromium metal film is slower, and when the mass fraction of the cerium oxide salt is higher than 25%, the etching rate of the chromium is overlarge to cause etching runaway, and the fineness of the etched circuit is obviously reduced. Specifically, the weight component of the cerium oxide salt may be typically, but not limited to 8%、8.2%、8.5%、8.7%、9%、9.2%、9.5%、9.7%、10%、10.2%、10.5%、10.7%、11%、11.2%、11.5%、11.7%、12%、12.5%、13%、13 .5%、14%、14 .5%、15%、15 .5%、16%、16.5%、17%、17 .5%、18%、18 .5%、19%、19 .5%、20%、20.5%、21%、21.5%、22%、23%、24% or 25% or the like, based on 100% of the total mass fraction of the etching solution.
In some embodiments, the cerium oxide salt is at least one selected from ammonium cerium nitrate, sodium cerium nitrate, potassium cerium nitrate, ammonium cerium sulfate, sodium cerium sulfate and potassium cerium sulfate, and the cerium oxide salt may be any one or more of the above, preferably ammonium cerium nitrate or a complex of ammonium cerium nitrate and ammonium cerium sulfate.
The organic sulfonic acid mainly provides an acidic environment for the strong oxidizing property of the oxidizing cerium salt such as ammonium cerium nitrate, and suppresses the adverse effect of the reduction of the oxidizing property caused by the hydrolysis reaction of the oxidizing cerium salt. In addition, the organic sulfonic acid can dissolve chromium and chromium oxide, thereby further improving the reaction rate and having the effects of reducing etching residues and inhibiting the increase of surface roughness.
The mass fraction of the organic sulfonic acid is 0.5% -9.5%, and the weight component of the organic sulfonic acid can be typically, but not limited to 0.5%、0.6%、0.7%、0.8%、0.9%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2%、2.1%、2.2%、2.3%、2.4%、2.5%、2.6%、2.7%、2.8％、2.9%、3.0％、3.1%、3.2％、3.3%、3.4％、3.5%、3.6％、3.7%、3.8%、3.9%、4％、4.2%、4.4%、4.6%、4.8％、5 %、5.2%、5.4、5.6％、5.8%、6%、6.2％、6.4％、6.5％、6.6%、6.7%、6.8%、6.9%、7%、7.1%、7.2%、7.3%、7.4%、7.5%、7.6%、7.7%、7.8%、7.9%、8.0%、8.1%、8.2%、8.3%、8.4%、8.5%、8.6%、8.7%、8.8%、8.9%、9.0%、9.1%、9.2%、9.3%、9.4%、9.5%% or the like based on the total mass fraction of the etching solution being 100%.
In some embodiments, the organic sulfonic acid is at least one selected from sulfamic acid, hydroxylamine sulfonic acid, hydroxyethyl sulfonic acid and 3-hydroxy propane sulfonic acid, and the organic sulfonic acid may be any one or more of the above, and each of the above organic sulfonic acids can increase the reaction rate while reducing etching residues and suppressing increase in surface roughness. The organic sulfonic acid is preferably sulfamic acid, hydroxylamine sulfonic acid or a complex of sulfamic acid and hydroxylamine sulfonic acid.
The peroxy compound has the function of synergizing the cerium salt and chromium oxide metal film, and meanwhile, the reduced Ce (III) ions in the etching solution can be further oxidized and returned to Ce (IV) ions, so that the recycling of the Ce (IV) ions is realized, and the purposes of recycling reactants and prolonging the etching service life are achieved.
The mass fraction of the peroxy compound is 2% -13%, and the weight component of the peroxy compound can be typically but not limited to 2%、2.2%、2.5%、2.7%、3%、3.3%、3.5%、3.7%、4%、4.2%、4.5%、4.7%、5%、5.5%、5.7%、6%、6.2%、6.5%、6.7%、7%、7.2%、7.5%、7.7%、8％、8.2%、8.5％、8.7%、9％、9.2%、9.5％、9.7%、10％、10.2%、10.5%、10.7%、11％、11.2%、11.5%、12%、13％ and the like based on the total mass fraction of the etching solution being 100%.
In some embodiments, the peroxy compound is at least one selected from urea peroxide, peracetic acid, sodium peroxide and sodium peroxycarbonate, and the peroxy compound can be any one or more of the above peroxy compounds, and each of the above peroxy compounds can prolong the etching service life. The peroxy compound is preferably urea peroxide, sodium peroxycarbonate or a compound of urea peroxide and sodium peroxycarbonate.
The stabilizer mainly improves the stability of the peroxy compound in the etching solution and inhibits the peroxy compound from being decomposed, so that the stability of the etching solution is further maintained, and the service life of the etching solution is further prolonged. The mass fraction of the stabilizer is as follows
When the mass percentage of the material is lower than 0.5 percent, the material cannot play a role in stabilizing the peroxy compound due to the excessively low content, the fineness of the etched circuit is obviously reduced, and when the mass percentage of the material is higher than 3.5 percent, the etching performance is reduced. The weight component of the stabilizer may be typically, but not limited to 0.5%、0.55%、0.6%、0.65%、0.7%、0.75%、0.8%、0.85%、0.9%、0.95%、1%、1.05%、1.1%、1.15%、1.2%、1.25%、1.3%、1.35%、1.4%、1.45%、1.5%、1.6%、1.7%、1.8%、1.9%、2%、2.1%、2.2%、2.3%、2.4%、2.5%、2.6％、2.7%、2.8％、2.9%、3％、3.1%、3.2、3.3％、3.4% or 3.5% or the like based on 100% total mass fraction of the etching solution.
In some embodiments, the stabilizer is selected from at least one of polyethylene glycol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol and 1, 10-decanediol, and the stabilizer can be any one or more of the above stabilizers, and the above stabilizers can play a role in stabilizing the peroxy compound and can inhibit the peroxy compound from decomposing. The stabilizer is preferably polyethylene glycol, and specifically at least one of polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 500 polyethylene glycol 600, and polyethylene glycol 800.
The functional ionic liquid has the functions of inhibiting side etching and improving the complexing ability of chromium ions in cooperation with the amino acid oligomer, thereby further playing the role of prolonging the service life of the etching liquid. The functional ionic liquid is at least one selected from amino-containing functional ionic liquid and hydroxyl-containing functional ionic liquid, and can be any one or more of the above. The amino or hydroxyl in the functionalized ionic liquid can form a chemical bond with the surface of the chromium metal film, so that a layer of protective film can be formed on the chromium metal film in the etching process, and meanwhile, the ionic liquid has a large-volume steric hindrance structure, so that the attack of etching liquid on the lateral chromium metal surface can be reduced, and the effect of controlling the line width loss is achieved. In addition, hydroxyl or amino functional groups in the functionalized ionic liquid can form complexes with chromium metal ions to reduce the concentration of free metal ions, thereby maintaining the stability and the service life of the etching solution.
When the mass percentage of the functionalized ionic liquid is 0.02% -1.0%, the lateral corrosion degree in the etching process cannot be effectively controlled, overetching is easy to occur, and defects such as circuit short circuit are caused, and when the mass percentage of the functionalized ionic liquid is higher than 1.0%, metal residues are possibly generated due to insufficient etching, and the risk of electric short circuit is further generated. The weight component of the functionalized ionic liquid may be typically, but not limited to 0.02%、0.03%、0.04%、0.05%、0.06%、0.07%、0.08%、0.09%、0.1%、0.15%、0.2%、0.25%、0.3%、0.35%、0.4%、0.45%、0.5%、0.55%、0.6%、0.65%、0.7%、0.75%、0.8%、0.85%、0.9%、0.95% or 1% or the like based on 100% total mass fraction of the etching liquid.
In some embodiments, the amino-containing functionalized ionic liquid is selected from at least one of 1-aminoethyl-3-methylimidazole nitrate, 1-aminoethyl-3-methylimidazole tetrafluoroborate, 1-aminoethyl-3-methylimidazole hexafluorophosphate, 1-aminoethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1-aminopropyl-3-methylimidazole nitrate, 1-aminopropyl-3-methylimidazole tetrafluoroborate, and 1-aminopropyl-3-methylimidazole hexafluorophosphate, and the amino-containing functionalized ionic liquid may be any one or more of the above.
In some embodiments, the hydroxyl-containing functionalized ionic liquid is selected from at least one of 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate, 1-hydroxyethyl-3-methylimidazolium hexafluorophosphate, 1-hydroxyethyl-3-methylimidazolium acetate, 1-hydroxyethyl-3-methylimidazolium p-toluenesulfonate, 1-hydroxyethyl-3-methylimidazolium bisulfate, 1-hydroxyethyl-3-methylimidazolium dihydrogen phosphate, 1-hydroxyethyl-2, 3-dimethylimidazole tetrafluoroborate, and 1-hydroxyethyl-2, 3-dimethylimidazole hexafluorophosphate, and the hydroxyl-containing functionalized ionic liquid may be any one or more of the above.
The amino acid-based oligomer has good water-solubility, and has higher complexing and adsorption performance than the traditional micromolecular carboxylic acid or amino acid complexing agent due to high-density carboxyl and amino functional groups on the molecular chain, so that free metal ions in the etching solution can be efficiently captured to form a complex, the concentration of the free metal ions in the etching solution is reduced, the natural decomposition loss of peroxy compounds is obviously reduced, and the purposes of maintaining the stability of the etching solution and prolonging the service life of the etching solution are achieved. In addition, the amino acid base oligomer provided by the embodiment of the invention can ionize and release a large number of hydrogen protons in carboxylic acid groups, so that the pH value fluctuation of the etching solution can be balanced and maintained, and the etching performance and the service life of the etching solution in a continuous etching process are further improved.
The mass fraction of the amino acid-based oligomer is 0.2% -2.5%, and the weight component of the amino acid-based oligomer may be typically, but not limited to 0.2%、0.25%、0.3%、0.35%、0.4%、045%、0.5%、0.55%、0.6%、0.65%、0.7%、0.75%、0.8%、0.85%、0.9%、0.95%、1%、1.05%、1.1%、1.15%、1.2%、1.25%、1.3%、1.35%、1.4%、1.45%、1.5%、1.6%、1.65%、1.7%、1.75%、1.8%、1.9%、2%、2.1%、2.2%、2.3%、2.4%% or 2.5% or the like, based on 100% of the total mass fraction of the etching solution.
In some embodiments, the amino acid based oligomer is a copolymer of an amino acid and an organic acid and has a number average molecular weight of 1500-4500, such as may be 1500, 2000, 2500, 3000, 3500, 4000, 4500, etc. The amino acid-based oligomer is selected from any one or more of aspartic acid-citric acid copolymer, serine-citric acid copolymer, lysine-citric acid copolymer, cysteine-citric acid copolymer, aspartic acid-malic acid copolymer, serine-malic acid copolymer, lysine-malic acid copolymer and cysteine-malic acid copolymer.
The pyrosulfate mainly has the effects of promoting etching reaction and increasing the solubility of metal salt so as to improve the metal ion load of an etching solution system and avoid the residual generated by the adsorption of metal ions on a substrate. The mass fraction of the pyrosulfate is 0.5% -3.5%, and the weight component of the pyrosulfate may be typically, but not limited to 0.5%、0.55%、0.6%、0.65%、0.7%、0.75%、0.8%、0.85%、0.9%、0.95%、1%、1.05%、1.1%、1.15%、1.2%、1.25%、1.3%、1.35%、1.4%、1.45%、1.5%、1.6%、1.65%、1.7%、1.75%、1.8%、1.85%、1.9%、1.95%、2%、2.1%、2.2%、2.3%、2.4%、2.5%、2.6%、2.7%、2.8%、2.9%、3%、3.1%、3.2%、3.3%、3.4%、3.5%、3.6%、3.7%、3.8%、3.9%、3.4%% or 3.5% or the like based on the total mass fraction of the etching solution being 100%.
In some embodiments, the pyrosulfate is at least one selected from sodium pyrosulfate, ammonium pyrosulfate and potassium pyrosulfate, and the pyrosulfate may be any one or more of the above, and the pyrosulfate is preferably ammonium pyrosulfate.
The alcohol ether solvent mainly plays a role in improving the solubility of the chromium metal complex, and as the etching reaction proceeds, the content of chromium ions in the etching solution is continuously increased, so that the problem of precipitation of the chromium metal complex is caused. The addition of the alcohol ether solvent is favorable for quickly dissolving the chromium metal complex before the precipitation of the chromium metal complex, improves the solubility of the complex, avoids precipitation residues of the complex, and further prolongs the service life of the etching solution.
The mass fraction of the alcohol ether solvent is 0.8% -5.5%, and the weight component of the alcohol ether solvent can be typically, but not limited to 0.8%、0.9%、1%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2%、2.1%、2.2%、2.3%、2.4%、2.5%、2.6%、2.7%、2.8%、2.9%、3%、3.1%、3.2%、3.3%、3.4%、3.5%、3.6%、3.7%、3.8%、3.9%、4%、4.1%、4.2%、4.3%、4.4%、4.5%、4.6%、4.7%、4.8%、5%、5.1%、5.2%、5.3%、5.4%、5.5% and the like, based on the total mass fraction of the etching solution being 100%.
In some embodiments, the alcohol ether solvents are at least one selected from ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether and triethylene glycol butyl ether, and the alcohol ether solvents can be any one or more of the above.
The Gemini surfactant has the main functions of reducing the dynamic and static surface tension of the etching solution, improving the affinity and wettability of the etching solution to the metal film to be etched, reducing the mass transfer resistance of the etching solution and improving the diffusion capacity of etching products in the etching solution, thereby improving the etching uniformity of the etching solution and reducing the etching load effect of different etching areas, and has good low-foaming performance and acid environment stability. In addition, the Gemini surfactant also has the effect of reducing burrs of etched circuits.
The mass fraction of the Gemini surfactant is 0.05% -2.5%, and the weight component of the Gemini surfactant can be typically but not limited to 0.05%、0.1%、0.15%、0.2%、0.25%、0.3%、0.35%、0.4%、0.45%、0.55%、0.6%、0.65%、0.7%、0.75%、0.8%、0.85%、0.9%、0.95%、1%、1.05%、1.1%、1.15%、1.2%、1.25%、1.3%、1.35%、1.4%、1.45%、1.5%、1.6%、1.65%、1.7%、1.75%、1.8%、1.85%、1.9%、1.95%、2%、2.1%、2.2%、2.3%、2.4%% or 2.5% based on 100% of the total mass fraction of the etching solution.
In some embodiments, the Gemini surfactant is selected from at least one of Surfynol420, surfynol440, surfynol465, and Surfynol485, and the Gemini surfactant may be any one or more of the above. The Gemini surfactant is preferably Surfynol420, surfynol440 or a complex of Surfynol420 and Surfynol 440.
The embodiment of the invention also provides a preparation method of the metal film wiring etching solution, which comprises the steps of mixing the cerium oxide salt, the organic sulfonic acid, the peroxy compound, the stabilizer, the functional ionic liquid, the amino acid-based oligomer, the pyrosulfate, the alcohol ether solvent, the Gemini surfactant and water according to the composition and the proportion of the metal film wiring etching solution, and optimizing the raw materials and the proportion to ensure that the prepared etching solution can regulate the etching rate, the etching profile and the pattern fineness of the etching solution on metal films with different specifications, and finally obtain the etching effects of low line width loss, good etching taper angle, no metal residue and smooth plane.
In some embodiments, the mixing temperature is controlled to be 20-40 ℃, such as 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃ and the like, the stirring speed is 80-200 r/min, such as 80r/min, 100r/min, 120r/min, 150r/min, 180r/min, 200r/min and the like, and the stirring time is 1h-2.5h, such as 1.0h, 1.5h, 2.0h, 2.5h and the like.
In the actual operation process, the raw materials which meet the composition of the metal film wiring etching solution can be placed into a PP or PTFE lining liquid preparation kettle with a circulating condensing device for stirring and mixing.
The embodiment of the invention also provides an etching method of the metal film wiring, which comprises the step of etching the glass substrate deposited with the metal film by utilizing the metal film wiring etching solution, and can obtain the etching effects of low line width loss, good etching taper angle, no metal residue and smooth plane due to the improvement of the composition of the metal film wiring etching solution.
In some embodiments, the glass substrate on which the metal film is deposited is immersed in the metal film wiring etching solution for etching, the etching temperature is controlled to be 25-55 ℃ (preferably 30-45 ℃), the etching time is controlled to be 50-175 sec, and the etching effect can be further improved by controlling the etching temperature and time.
Specifically, the etching temperature may be 25 ℃,30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, etc., and the etching time may be 50sec, 80sec, 100sec, 120sec, 150sec, 170sec, 175sec, etc., with sec representing second.
In some embodiments, the metal film is a chromium or chromium-based composite film, such as any one of a chromium-aluminum, chromium-nickel, chromium-molybdenum, and chromium-niobium alloy film, and any one or more of the above. The thickness of the metal film is 800 a-7500 a, for example, 800 a, 1000 a, 1500 a, 2000 a, 2500 a, 3000 a, 3500 a, 4000 a, 4500 a, 5000 a, 5500 a, 6000 a, 6500 a, 7000 a, 7500 a, etc.
The embodiment of the invention also provides a metal film wiring etching solution which is used for electrode material wiring etching, wiring material wiring etching or film stripping reworking in the manufacture of a thin film transistor liquid crystal display (TFT-LCD) and an organic light emitting diode display (OLED). When the etching effect is poor, the film removing reworking is used for removing the metal film on the surface, and returning to prepare again so as to avoid waste of devices.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Examples 1 to 12 and comparative examples 1 to 11
Examples 1 to 12 and comparative examples 1 to 11 provided metal film wiring etching solutions, respectively, the compositions of examples 1 to 12 are shown in Table 1, and the compositions of comparative examples 1 to 11 are shown in Table 2.
TABLE 1 composition of etching solutions in examples 1-12
TABLE 2 composition of etching solutions in comparative examples 1 to 11
Raw material interpretation in table 1:
y1-ceric ammonium nitrate;
y2-ceric ammonium sulfate;
h1-sulfamic acid;
h2-hydroxylamine sulfonic acid;
g1-carbamide peroxide;
g2-sodium peroxycarbonate;
PEG 600-polyethylene glycol 600;
TEG-triethylene glycol;
l1-aminoethyl-3-methylimidazole tetrafluoroborate;
L2-1-hydroxyethyl-3-methylimidazole bisulfate;
a1-aspartic acid-citric acid copolymer, M n =3500
A2-aspartic acid-malic acid copolymer, M n =3500.
APS-ammonium pyrosulfate;
2-BE-ethylene glycol butyl ether;
DBG-diethylene glycol butyl ether;
Ge1─Surfynol420;
Ge2─Surfynol440。
the preparation method of the etching solution provided by each embodiment and comparative example comprises the following steps:
Weighing cerium oxide salt, organic sulfonic acid, peroxy compound, stabilizer, functional ionic liquid, amino acid base oligomer, pyrosulfate, alcohol ether solvent, gemini surfactant and ultrapure water according to the material formula and mass ratio, mixing and preparing to obtain metal film wiring etching solution, wherein the etching solution is placed into a PP or PTFE lining solution preparation kettle with a circulating condensing device to be stirred and mixed, the temperature of the kettle solution is controlled at 30 ℃, the stirring speed is 100r/min, and the stirring time is 1.5h.
In order to compare technical effects of each example and comparative example, the following experimental examples were specially set.
Experimental example 1 etching Rate test
A chromium metal film layer having a thickness of 480nm was deposited on a 0.8mm glass substrate, a resist layer was spin-coated on the chromium metal film, and exposure and development patterning were performed (specific steps: ① coating: spin-coating a positive photoresist, ② pre-bake: hot plate temperature controlled at 90 ℃ and bake time 90sec; ③ exposure: i-line lithography machine exposure 80mj/cm; ④ development: 2.38% TMAH solution development 60sec; ⑤ post-bake: hot plate temperature controlled at 110 ℃ and bake time 120 sec), and then water rinsing and drying were performed after etching for 1min in the chromium etching solutions prepared in examples and comparative examples, and etching amounts were measured by stylus type step differences, and etching rates (unit nm/min): etching rate=etching amounts/etching times).
Experimental example 2 etching Effect test
A chromium metal film layer with a thickness of 480nm was deposited on a glass substrate, a photoresist layer was spin-coated on the chromium metal film, and subjected to exposure and development patterning, and then 1.2 x JET (JET is an etching time just completed) was etched in the chromium etching solutions prepared in examples and comparative examples at 40 ℃ for a multiple time, and then rinsed with water and dried, and a part of the substrate was observed for a slice section by a scanning electron microscope, CD losss was measured, and a part was photoresist-removed and water-washed dried by a photoresist stripper, and then observed for metal residues, edge burrs, chromium metal line surface smoothness, and photoresist penetration by a scanning electron microscope. The evaluation criteria are as follows:
Metal residue evaluation, delta-no residue present, -, small amount of residue present, -, large amount of residue present;
Line edge burr evaluation, namely O-no obvious burrs, B, +_ slight burrs, X, -, obvious burrs or flaws;
Single sided CD loss evaluation: I-CD loss is less than or equal to 0.3um, II-0.3um < CD; less than or equal to 0.4um, III-CD loss >0.4um;
The surface smoothness is that the four-surface has no obvious defect, the surface roughness is smaller, the gamma surface roughness is larger;
The penetration condition of the etching resistant layer is that the etching resistant layer is in the shape of ∈ -no obvious penetration trace, ■ -a small amount of penetration trace and x-a large amount of penetration trace.
TABLE 3 etching rate and etching effect test results of the etching solutions of examples and comparative examples
As can be seen from Table 3, the overall properties of comparative examples 1 to 11 are significantly inferior to those of examples 1 to 11, and the comparative examples show metal residues, line edge burrs, surface smoothness degradation, penetration marks, and the like.
Experimental example 3 etching solution Life test
Chromium powder was added to each of the etching solutions of examples 1 to 3, example 12, comparative example 4, comparative example 7 and comparative example 11 to dissolve, the etching of the chromium metal film was performed at a concentration of 500ppm per rise in the etching solution, the etching time was controlled to 1.2 x jet, and the etching temperature was controlled to 40 ℃, and when the etching effect did not reach the desired requirement (no etching residue, no apparent penetration, no apparent defect in the chromium metal wire, single CD loss was not more than 0.4) as the chromium concentration increased, the copper ion content was considered to have exceeded its lifetime.
Experimental example 4 etching solution stability test
6000Ppm chromium powder was slowly added to each of the etching solutions of examples 1 to 3, example 12, comparative example 4, comparative example 7 and comparative example 11 to sufficiently dissolve, and then the etching solutions were allowed to stand at room temperature for 72 hours, and then whether crystals were precipitated in the etching solution samples was observed.
TABLE 4 etchant Life and stability test results
As is clear from the results of tables 3 and 4, the etching solutions of examples 1 to 12 of the present invention all exhibited good etching properties, and no phenomena of metal residue, line edge burr, excessive single-sided CD loss, penetration of resist layer, and increased roughness of wiring surface were observed.
It is apparent from examples 1 and 1 that, when the content of the organic sulfonic acid component in the etching solution is low, the oxidizing ability of the cerium oxide is insufficient due to the shortage of the acidic environment in the etching solution, and in addition, the organic sulfonic acid has the effect of dissolving chromium and chromium oxide, and when the system organic sulfonic acid is low, the etching rate is slow, the soaking time of the resist layer in the etching solution is prolonged, and the adverse phenomena of penetration of the etching solution and increase of the metal surface roughness are caused, and further, as is apparent from comparative examples 1 and 2, when the content of the organic sulfonic acid is too high, the etching rate is too fast and out of control, and further, the etching result of etching CD loss and edge burr is generated, and the molecular chain of the resist layer is damaged due to the organic sulfonic acid with the same high content, and further, the adverse effects of penetration and increase of the metal surface roughness are generated.
As can be seen from example 1 and comparative example 3, the Gemini surfactant plays a positive role in controlling the fineness of the etched circuit and the penetration of the resist layer against the etching solution.
As can be seen from example 1 and comparative example 4, the etching life of the etching solution of comparative example 4 without the stabilizer component is significantly low, and the stability of the etching solution is significantly reduced.
As is clear from comparative examples 1,3, 5 and 6, the ionic liquid has an obvious effect of suppressing the amount of side etching of the wiring during etching, and the amount of side etching of the etching liquid of comparative example 5 without the ionic liquid component is significantly larger than that of example 1, whereas the content of ionic liquid exceeding the limit content of the present invention also causes a slow etching rate and also causes etching residues.
As is clear from comparative examples 1, 7 and 8, comparative example 7 having a content of a peroxy compound lower than the range defined by the present invention has a problem of a low etching life, whereas comparative example 8 having a content of a peroxy compound higher than the range defined by the present invention has a poor etching effect.
As is clear from the etching results of comparative examples 1, 9 and 10, the effect of the cerium oxide salt on the etching rate was remarkable, and when the content thereof was below the range defined in the present invention, the problem of slow etching rate was exhibited, and the adverse results of etching residue, penetration of the resist layer and increase in the roughness of the metal surface were finally produced, whereas when the content thereof was above the range defined in the present invention, the good etching results were not obtained.
As is clear from comparative examples 3 and 11, the alcohol ether solvent has a remarkable influence on the life and stability of the etching liquid, whereas the etching life of the etching liquid of comparative example 11 in which the alcohol ether solvent is not used is remarkably lower than that of example 3, and the stability of the etching liquid is deteriorated.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The metal film wiring etching solution is characterized by comprising, by mass, 8% -25% of cerium oxide salt, 0.5% -9.5% of organic sulfonic acid, 2% -13% of peroxy compound, 0.5% -3.5% of stabilizer, 0.02% -1.0% of functionalized ionic liquid, 0.2% -2.5% of amino acid-based oligomer, 0.5% -3.5% of pyrosulfate, 0.8% -5.5% of alcohol ether solvent, 0.05% -2.5% of Gemini surfactant and the balance of water;
The cerium oxide salt is at least one selected from ammonium cerium nitrate, sodium cerium nitrate, potassium cerium nitrate, ammonium cerium sulfate, sodium cerium sulfate and potassium cerium sulfate;
the organic sulfonic acid is at least one selected from sulfamic acid, hydroxylamine sulfonic acid, hydroxyethyl sulfonic acid and 3-hydroxy propane sulfonic acid;
the peroxy compound is at least one selected from carbamide peroxide, peracetic acid, sodium peroxide and sodium peroxycarbonate;
The stabilizer is at least one selected from polyethylene glycol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol and 1, 10-decanediol;
The functional ionic liquid is at least one selected from amino-containing functional ionic liquid and hydroxyl-containing functional ionic liquid; the amino-containing functional ionic liquid is selected from at least one of 1-aminoethyl-3-methylimidazole nitrate, 1-aminoethyl-3-methylimidazole tetrafluoroborate, 1-aminoethyl-3-methylimidazole hexafluorophosphate, 1-aminoethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1-aminopropyl-3-methylimidazole nitrate, 1-aminopropyl-3-methylimidazole tetrafluoroborate and 1-aminopropyl-3-methylimidazole hexafluorophosphate, and the hydroxyl-containing functional ionic liquid is selected from at least one of 1-hydroxyethyl-3-methylimidazole tetrafluoroborate, 1-hydroxyethyl-3-methylimidazole hexafluorophosphate, 1-hydroxyethyl-3-methylimidazole acetate, 1-hydroxyethyl-3-methylimidazole p-toluenesulfonate, 1-hydroxyethyl-3-methylimidazole hydrogen sulfate, 1-hydroxyethyl-3-methylimidazole dihydrogen phosphate, 1-hydroxyethyl-2, 3-dimethylimidazole tetrafluoroborate and 1-hydroxyethyl-2, 3-dimethylimidazole hexafluorophosphate;
the amino acid base oligomer is a copolymer of amino acid and organic acid, and has a number average molecular weight of 1500-4500, wherein the amino acid base oligomer is selected from at least one of aspartic acid-citric acid copolymer, serine-citric acid copolymer, lysine-citric acid copolymer, cysteine-citric acid copolymer, aspartic acid-malic acid copolymer, serine-malic acid copolymer, lysine-malic acid copolymer and cysteine-malic acid copolymer;
The pyrosulfate is at least one selected from sodium pyrosulfate, ammonium pyrosulfate and potassium pyrosulfate;
The alcohol ether solvents are at least one selected from ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether and triethylene glycol butyl ether;
The Gemini surfactant is at least one selected from Surfynol420, surfynol440, surfynol465 and Surfynol 485.
2. The metal film wiring etching liquid according to claim 1, wherein the metal film wiring etching liquid comprises, by mass, 12% -23% of an oxidizing cerium salt, 2% -8% of an organic sulfonic acid, 3.5% -11% of a peroxy compound, 0.8% -2.5% of a stabilizer, 0.1% -0.85% of a functionalized ionic liquid, 0.5% -2.0% of an amino acid-based oligomer, 0.85% -2.5% of a pyrosulfate, 1% -4.5% of an alcohol ether solvent, 0.1% -1.5% of a Gemini surfactant, and the balance of water.
3. A method for producing a metal film wiring etching solution according to any one of claims 1 to 2, comprising mixing the cerium oxide salt, the organic sulfonic acid, the peroxy compound, the stabilizer, the functionalized ionic liquid, the amino acid-based oligomer, the pyrosulfate, the alcohol ether solvent, the Gemini surfactant and water according to the composition and the ratio of the metal film wiring etching solution.
4. A method according to claim 3, wherein the mixing temperature is controlled to be 20 ℃ to 40 ℃, the stirring speed is 80r/min to 200r/min, and the stirring time is 1h to 2.5h.
5. A method for etching a metal film wiring, comprising etching a glass substrate on which a metal film is deposited by using the metal film wiring etching liquid according to any one of claims 1 to 2.
6. The etching method according to claim 5, wherein the glass substrate on which the metal film is deposited is immersed in the metal film wiring etching liquid for etching, the etching temperature is controlled to be 25 ℃ to 55 ℃ and the etching time is controlled to be 50sec to 175sec.
7. The method of claim 6, wherein the metal film is a chromium or chromium-based composite film, and the metal film has a thickness of 800 a-7500 a.
8. The metal film wiring etching liquid according to any one of claims 1 to 2, which is used for electrode material wiring etching, wiring material wiring etching or film-removing reworking in the manufacture of a thin film transistor liquid crystal display or an organic light emitting diode display.
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