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US20190323129A1 - Etching solution composition - Google Patents

Etching solution composition Download PDF

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Publication number
US20190323129A1
US20190323129A1 US16/074,777 US201816074777A US2019323129A1 US 20190323129 A1 US20190323129 A1 US 20190323129A1 US 201816074777 A US201816074777 A US 201816074777A US 2019323129 A1 US2019323129 A1 US 2019323129A1
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US
United States
Prior art keywords
solution composition
etching
etching solution
acid
mass proportion
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US16/074,777
Inventor
Jia Li
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TCL China Star Optoelectronics Technology Co Ltd
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Shenzhen China Star Optoelectronics Technology Co Ltd
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Assigned to SHENZHEN CHINA STAR OPTOELECTRONICS TECHNOLOGY CO., LTD. reassignment SHENZHEN CHINA STAR OPTOELECTRONICS TECHNOLOGY CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LI, JIA
Publication of US20190323129A1 publication Critical patent/US20190323129A1/en
Abandoned legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • 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
    • C23F1/32—Alkaline compositions
    • C23F1/34—Alkaline 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
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • 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
    • C23F1/32—Alkaline compositions
    • C23F1/40—Alkaline compositions for etching other metallic material

Definitions

  • the present invention relates to a display technology, and more particularly to an etching solution composition.
  • Microcircuits such as semiconductor devices, TFT-LCDs, OLEDs are made by a series of lithography steps, including evenly applying photoresist on a conductive metal film such as aluminum, aluminum alloy, copper, or copper alloy, or on an insulating film such as silicon dioxide film or silicon nitride film formed on a substrate, and then imaging after light irradiating through a thin film having patterns so as to image the desired patterns. After dry etching or a wet etching is used to develop the patterns on the metal film or the insulating film below the photoresist, stripping is used to remove unwanted photoresist.
  • a conductive metal film such as aluminum, aluminum alloy, copper, or copper alloy
  • an insulating film such as silicon dioxide film or silicon nitride film formed on a substrate
  • stripping is used to remove unwanted photoresist.
  • Copper alloys of gate electrodes and metallic data wires in large-sized displays compared with aluminum chromium wires in past technology, have low impedance and no environmental issues.
  • the copper has problems, such as low adherence to the glass substrate and the insulating film, and is easy to diffuse into silicon oxide film, so that Ti and Mo are usually used as lower thin-film metals.
  • etching uniformity of the current etching solution is difficult to be controlled during the etching process, and results in loss of properties such as etching tapered angles, etching deviation, and etching straightness, so that product quality is affected.
  • An object of the present invention is to provide an etching solution composition, which can adjust an etching speed to avoid loss of properties such as etching taper angles, an etching deviation, and an etching straightness, and thus the product quality can be enhanced.
  • the present invention provides an etching solution composition, comprising hydrogen peroxide, an etching inhibitor, a chelating agent, an etching additive, fluorides, a stabilizer, and water; wherein in the etching solution composition, a mass proportion of the hydrogen peroxide is 4% to 25%, a mass proportion of the etching inhibitor is 6% to 10%, a mass proportion of the chelating agent is 0.01% to 20%, a mass proportion of the etching additive is 0.01% to 20%, a mass proportion of the fluorides is 0.01% to 20%, a mass proportion of the stabilizer is 0.01% to 5%, and a mass proportion of water is to allow a total mass proportion of the etching solution composition to be 100%;
  • the etching inhibitor is one or more of a heterocyclic aromatic compound, a heterocyclic aliphatic compound, an aromatic polyol, an ammonia monohydrate, quinoline, and a linear polyol; and the stabilizer is one or more of ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, ethanol, and isopropanol.
  • the mass proportion of the chelating agent in the etching solution composition is 6% to 20%.
  • the mass proportion of the etching additive in the etching solution composition is 6% to 20%.
  • the mass proportion of the fluorides in the etching solution composition is 6% to 20%.
  • the mass proportion of the stabilizer in the etching solution composition is 3% to 5%.
  • the etching additive is one or more of an organic acid, an inorganic acid, an organic acid salt, and an inorganic acid salt.
  • the chelating agent is one or more of iminodiacetic acid, nitrilotriacetic acid, ethylenediamine tetraacetic acid, diethylene triamine pentaacetic acid, methylene phosphate, aetidronic acid, ethylenediamine tetraacetic acid, diethylenetriamine, sarcosine, alanine, aminobutyric acid, glutamate, glycine, 1-diphosphonic acid, an organic polyphosphonic acid, and ethylenediamine tetraacetic acid.
  • the fluorides are compounds which dissociate fluoride ions.
  • the present invention provides an etching solution composition, comprising: hydrogen peroxide, an etching inhibitor, a chelating agent, an etching additive, fluorides, a stabilizer, and water;
  • a mass proportion of the hydrogen peroxide is 4% to 25%
  • a mass proportion of the etching inhibitor is 6% to 10%
  • a mass proportion of the chelating agent is 0.01% to 20%
  • a mass proportion of the etching additive is 0.01% to 20%
  • a mass proportion of the fluorides is 0.01% to 20%
  • a mass proportion of the stabilizer is 0.01% to 5%
  • a mass proportion of water is to allow a total mass proportion of the etching solution composition to be 100%.
  • the mass proportion of the chelating agent in the etching solution composition is 6% to 20%.
  • the mass proportion of the etching additive in the etching solution composition is 6% to 20%.
  • the mass proportion of the fluorides in the etching solution composition is 6% to 20%.
  • the mass proportion of the stabilizer in the etching solution composition is 3% to 5%.
  • the etching inhibitor is one or more of a heterocyclic aromatic compound, a heterocyclic aliphatic compound, an aromatic polyol, an ammonia monohydrate, quinoline, and a linear polyol.
  • the etching additive is an organic acid, and inorganic acid, and organic acid salt, and an inorganic acid salt.
  • the chelating agent is one or more of iminodiacetic acid, nitrilotriacetic acid, ethylenediamine tetraacetic acid, diethylene triamine pentaacetic acid, methylene phosphate, etidronic acid, ethylenediamine tetraacetic acid, diethylenetriamine, sarcosine, alanine, aminobutyric acid, glutamate, glycine, 1-diphosphonic acid, an organic polyphosphonic acid, and ethylenediamine tetraacetic acid.
  • the stabilizer is one or more of ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, ethanol, and isopropanol.
  • the fluorides are compounds which dissociate fluoride ions.
  • the beneficial effects of the present invention are: an etching solution composition comprising hydrogen peroxide, an etching inhibitor, a chelating agent, an etching additive, fluorides, a stabilizer, and water.
  • the etching uniformity is increased by adjusting a mass proportion of each component in the etching solution composition, so as to avoid loss of properties such as etching taper angles, an etching deviation, and an etching straightness, thereby enhancing the product quality.
  • An etching solution composition according to one embodiment of the present invention can simultaneously etch copper/molybdenum film (Cu/Mo film) or copper/molybdenum alloy film (Cu/Mo alloy film).
  • Cu/Mo film herein is referred to copper film and molybdenum film
  • Cu/Mo alloy film herein is referred to copper film and molybdenum alloy film.
  • the molybdenum alloy is an alloy of molybdenum and various metals, preferably an alloy of molybdenum and titanium (Ti), tantalum (Ta), chromium (Cr), neodymium (Nd), nickel (Ni), indium (In), or tin (Sn), more preferably an alloy of molybdenum and titanium.
  • An etching solution composition comprises: hydrogen peroxide, an etching inhibitor, a chelating agent, an etching additive, fluorides, a stabilizer, and water; wherein in the etching solution composition, a mass proportion of the hydrogen peroxide is 4% to 25%, a mass proportion of the etching inhibitor is 6% to 10%, a mass proportion of the chelating agent is 0.01% to 20%, a mass proportion of the etching additive is 0.01% to 20%, a mass proportion of the fluorides is 0.01% to 20%, a mass proportion of the stabilizer is 0.01% to 5%, and a mass proportion of water is to allow a total mass proportion of the etching solution composition to be 100%.
  • the hydrogen peroxide is served as a main oxidant of the Cu/Mo metal or Cu/Mo alloy.
  • the mass proportion of the hydrogen peroxide in the etching solution composition is 4% to 25%.
  • the mass proportion of the hydrogen peroxide is less than 4%, the acidification of the Cu/Mo alloy will be insufficient, so that the etching cannot be executed.
  • the mass proportion of the hydrogen peroxide exceeds 25%, the etching speed will be so fast, such that it is difficult to control the progress of the process.
  • the etching inhibitor can adjust the etching speed of Cu/Mo metal or Cu/Mo alloy to allow them to form the etching profile with appropriate taper angles.
  • the mass proportion of the etching inhibitor is 6% to 10%.
  • the mass proportion of the etching inhibitor is less than 6%, the performance of adjusting the taper angles will be reduced.
  • the mass proportion of the etching inhibitor exceeds 10%, the etching speed will slow down, and then the engineering efficiency is affected.
  • the etching inhibitor can be one or more of a heterocyclic aromatic compound, a heterocyclic aliphatic compound, an aromatic polyol, an ammonia monohydrate, quinoline, and a linear polyol; and the stabilizer is one or more of ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, ethanol, and isopropanol.
  • the heterocyclic aromatic compound can be furan, thiophene, pyrrole, oxazole, thiazole, pyrazole, triazole, tetrazole, benzofuran, benzothiophene, indole, benzothiazole, benzoimidazole, benzopyrazole, aminotetrazole, or methyl.
  • the heterocyclic aliphatic compound can be piperazine, methyl piperazine, pyrrolidine, or alloxan.
  • the aromatic polyol can be gallic acid, methyl ester, ethyl ester, propanol salt, or butyl ester.
  • the linear polyol can be polyol from glycerol, erythritol, sorbitol, mannitol, or xylitol.
  • the chelating agent forms chelation with the copper and molybdenum ions generated during etching and deactivates them, so as to inhibit the decomposition of hydrogen peroxide in the etching solution.
  • the metallic ions which are acidized cannot be deactivated during etching.
  • the acidized metallic ions can facilitate decomposition of the hydrogen peroxide in the etching solution composition and cause heat and explosion.
  • the mass proportion of the chelating agent in the etching solution composition is 0.01% to 20%, and the mass proportion of the chelating agent in the etching solution composition is more preferably 6% to 20%.
  • the mass proportion of the chelating agent is less than 0.01%, amount of the metallic ions to be deactivated is very few, and thus the performance of inhibiting the decomposition of the hydrogen peroxide will be reduced. If the mass proportion of the chelating agent exceeds 20%, the excess chelation is formed, and then the effect of deactivation of the metallic ions is poor and the engineering efficiency is affected.
  • the chelating agent can be one or more of iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylene triamine pentaacetic acid, methylene phosphate, etidronic acid, ethylenediaminetetraacetic acid, diethylenetriamine, sarcosine, alanine, aminobutyric acid, glutamate, glycine, 1-diphosphonic acid, an organic polyphosphonic acid, and ethylenediaminetetraacetic acid.
  • an etching additive can also be included.
  • the etching additive can be a surfactant for promoting the etching performance.
  • the mass proportion of the etching additive in the etching solution composition is 0.01% to 20%; more preferably, the mass proportion of the etching additive in the etching solution composition is 6% to 20%.
  • the etching additive can be one or more of an organic acid, an inorganic acid, an organic acid salt, and an inorganic acid salt, wherein the organic acid can be acetic acid, formic acid, butyric acid, citric acid, glycolic acid, oxalic acid, 1,3-propanedioic acid, pentanoic acid, propionic acid, tartaric acid, gluconic acid, glycine, succinic acid, butanedioic acid, alkyl methanesulfonic acid, alkyl benzenesulfonic acid, alkyl diphenyl ether disulfonic acid, alkyl naphthalenesulfonic acid, naphthalenesulfonic acid, naphthalene disulfonic acid, polymer of formaldehyde and naphthalenesulfonic acid, polymer of acrylamide methyl propane sulfonic acid, acrylic acid, sulfonic acid group of vinyl
  • the inorganic acid can be nitric acid, sulfuric acid, hydrochloric acid, hypochlorous acid, permanganic acid, phosphoric acid, boric acid, hyposulfurous acid, perchloric acid, permonosulfuric acid, peroxydisulfuric acid, or peroxydicarbonic acid.
  • the fluorides can enhance the etching speed of the Mo alloy when the Cu/Mo alloy is etched simultaneously, and reduce the length of tails in order to remove the residue of the Mo alloy generated during etching. If the tail of the Mo alloy increases, it will reduce the brightness. The residues remaining on the substrate and the lower film will cause electrical short-circuiting, poor wiring, and reduced brightness. Therefore, the residues must be removed.
  • the mass proportion of the fluorides in the etching solution composition is 0.01% to 20%, and more preferably, the mass proportion of the fluorides is 6% to 20%. When the mass proportion of the fluorides is less than 0.01%, the residues of the Mo alloy cannot be removed efficiently. When the mass proportion of the fluorides exceeds 20%, the lower film will be etched.
  • the fluorides according to one embodiment of the present invention are compounds which dissociate fluoride ions, which can be hafnium fluoride, sodium fluoride, potassium fluoride, aluminum fluoride, fluoroboric acid, ammonium fluoride, ammonium hydrogen difluoride, sodium bifluoride, potassium bifluoride, or ammonium fluoroborate. It is also possible to use one or more of the above fluorides at the same time.
  • the stabilizer is to control the decomposition of the hydrogen peroxide when the etching process is repeated and the content of the metallic ions in the etching solution is high.
  • Amines can inhibit the decomposition of the hydrogen peroxide caused by the increased concentration of the metallic ions in the etching process, and have the effect of maintaining the etching properties for a long period of time.
  • the etching stabilizer used in the present invention has larger hydrophilicity and has the effect for inhibiting the formation of the metallic residue.
  • the mass proportion of the stabilizer in the etching solution composition is 0.01% to 5%, and more preferably, the mass proportion of the stabilizer is 3% to 50%.
  • the stabilizer can be one or more of ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, ethanol, and isopropanol.
  • the etching solution composition of the present invention can be used for etching the Cu/Mo alloy film of electrodes of TFT-LCD display or OLED.
  • the metallic ions can be stabilized to control the decomposition of the hydrogen peroxide and increase the number of etching cycles and etching capacity, as well as maintain the etching properties such as etching taper angles, the etching deviation, and the etching straightness, so that the amount of the etching solution used in the etching process can be reduced and then the producing cost of TFT-LCD and OLED can be reduced significantly.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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Abstract

An etching solution composition of this disclosure contains hydrogen peroxide, an etching inhibitor, a chelating agent, an etching additive, fluorides, a stabilizer, and water. Etching uniformity is increased by adjusting a mass proportion of each component in the etching solution composition, so as to avoid loss of properties such as etching tapered angles, etching deviation, and etching straightness, thereby enhancing product quality.

Description

    FIELD OF INVENTION
  • The present invention relates to a display technology, and more particularly to an etching solution composition.
    • BACKGROUND OF INVENTION
  • Microcircuits, such as semiconductor devices, TFT-LCDs, OLEDs are made by a series of lithography steps, including evenly applying photoresist on a conductive metal film such as aluminum, aluminum alloy, copper, or copper alloy, or on an insulating film such as silicon dioxide film or silicon nitride film formed on a substrate, and then imaging after light irradiating through a thin film having patterns so as to image the desired patterns. After dry etching or a wet etching is used to develop the patterns on the metal film or the insulating film below the photoresist, stripping is used to remove unwanted photoresist.
  • Copper alloys of gate electrodes and metallic data wires in large-sized displays, compared with aluminum chromium wires in past technology, have low impedance and no environmental issues. The copper has problems, such as low adherence to the glass substrate and the insulating film, and is easy to diffuse into silicon oxide film, so that Ti and Mo are usually used as lower thin-film metals.
  • However, etching uniformity of the current etching solution is difficult to be controlled during the etching process, and results in loss of properties such as etching tapered angles, etching deviation, and etching straightness, so that product quality is affected.
    • SUMMARY OF INVENTION
  • An object of the present invention is to provide an etching solution composition, which can adjust an etching speed to avoid loss of properties such as etching taper angles, an etching deviation, and an etching straightness, and thus the product quality can be enhanced.
  • For solving above problems, technical solutions of the present invention is as follows:
  • The present invention provides an etching solution composition, comprising hydrogen peroxide, an etching inhibitor, a chelating agent, an etching additive, fluorides, a stabilizer, and water; wherein in the etching solution composition, a mass proportion of the hydrogen peroxide is 4% to 25%, a mass proportion of the etching inhibitor is 6% to 10%, a mass proportion of the chelating agent is 0.01% to 20%, a mass proportion of the etching additive is 0.01% to 20%, a mass proportion of the fluorides is 0.01% to 20%, a mass proportion of the stabilizer is 0.01% to 5%, and a mass proportion of water is to allow a total mass proportion of the etching solution composition to be 100%;
  • wherein the etching inhibitor is one or more of a heterocyclic aromatic compound, a heterocyclic aliphatic compound, an aromatic polyol, an ammonia monohydrate, quinoline, and a linear polyol; and the stabilizer is one or more of ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, ethanol, and isopropanol.
  • In the etching solution composition of the present invention, the mass proportion of the chelating agent in the etching solution composition is 6% to 20%.
  • In the etching solution composition of the present invention, the mass proportion of the etching additive in the etching solution composition is 6% to 20%.
  • In the etching solution composition of the present invention, the mass proportion of the fluorides in the etching solution composition is 6% to 20%.
  • In the etching solution composition of the present invention, the mass proportion of the stabilizer in the etching solution composition is 3% to 5%.
  • In the etching solution composition of the present invention, the etching additive is one or more of an organic acid, an inorganic acid, an organic acid salt, and an inorganic acid salt.
  • In the etching solution composition of the present invention, the chelating agent is one or more of iminodiacetic acid, nitrilotriacetic acid, ethylenediamine tetraacetic acid, diethylene triamine pentaacetic acid, methylene phosphate, aetidronic acid, ethylenediamine tetraacetic acid, diethylenetriamine, sarcosine, alanine, aminobutyric acid, glutamate, glycine, 1-diphosphonic acid, an organic polyphosphonic acid, and ethylenediamine tetraacetic acid.
  • In the etching solution composition of the present invention, the fluorides are compounds which dissociate fluoride ions.
  • The present invention provides an etching solution composition, comprising: hydrogen peroxide, an etching inhibitor, a chelating agent, an etching additive, fluorides, a stabilizer, and water;
  • wherein, in the etching solution composition, a mass proportion of the hydrogen peroxide is 4% to 25%, a mass proportion of the etching inhibitor is 6% to 10%, a mass proportion of the chelating agent is 0.01% to 20%, a mass proportion of the etching additive is 0.01% to 20%, a mass proportion of the fluorides is 0.01% to 20%, a mass proportion of the stabilizer is 0.01% to 5%, and a mass proportion of water is to allow a total mass proportion of the etching solution composition to be 100%.
  • In the etching solution composition of the present invention, the mass proportion of the chelating agent in the etching solution composition is 6% to 20%.
  • In the etching solution composition of the present invention, the mass proportion of the etching additive in the etching solution composition is 6% to 20%.
  • In the etching solution composition of the present invention, the mass proportion of the fluorides in the etching solution composition is 6% to 20%.
  • In the etching solution composition of the present invention, the mass proportion of the stabilizer in the etching solution composition is 3% to 5%.
  • In the etching solution composition of the present invention, the etching inhibitor is one or more of a heterocyclic aromatic compound, a heterocyclic aliphatic compound, an aromatic polyol, an ammonia monohydrate, quinoline, and a linear polyol.
  • In the etching solution composition of the present invention, the etching additive is an organic acid, and inorganic acid, and organic acid salt, and an inorganic acid salt.
  • In the etching solution composition of the present invention, the chelating agent is one or more of iminodiacetic acid, nitrilotriacetic acid, ethylenediamine tetraacetic acid, diethylene triamine pentaacetic acid, methylene phosphate, etidronic acid, ethylenediamine tetraacetic acid, diethylenetriamine, sarcosine, alanine, aminobutyric acid, glutamate, glycine, 1-diphosphonic acid, an organic polyphosphonic acid, and ethylenediamine tetraacetic acid.
  • In the etching solution composition of the present invention, the stabilizer is one or more of ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, ethanol, and isopropanol.
  • In the etching solution composition of the present invention, the fluorides are compounds which dissociate fluoride ions.
  • The beneficial effects of the present invention are: an etching solution composition comprising hydrogen peroxide, an etching inhibitor, a chelating agent, an etching additive, fluorides, a stabilizer, and water. The etching uniformity is increased by adjusting a mass proportion of each component in the etching solution composition, so as to avoid loss of properties such as etching taper angles, an etching deviation, and an etching straightness, thereby enhancing the product quality.
    • BRIEF DESCRIPTION OF DRAWINGS
  • Figure US20190323129A1-20191024-P00999
    • DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
  • An etching solution composition according to one embodiment of the present invention can simultaneously etch copper/molybdenum film (Cu/Mo film) or copper/molybdenum alloy film (Cu/Mo alloy film). The “Cu/Mo film” herein is referred to copper film and molybdenum film; The “Cu/Mo alloy film” herein is referred to copper film and molybdenum alloy film. The molybdenum alloy is an alloy of molybdenum and various metals, preferably an alloy of molybdenum and titanium (Ti), tantalum (Ta), chromium (Cr), neodymium (Nd), nickel (Ni), indium (In), or tin (Sn), more preferably an alloy of molybdenum and titanium.
  • An etching solution composition according to one embodiment of the present invention comprises: hydrogen peroxide, an etching inhibitor, a chelating agent, an etching additive, fluorides, a stabilizer, and water; wherein in the etching solution composition, a mass proportion of the hydrogen peroxide is 4% to 25%, a mass proportion of the etching inhibitor is 6% to 10%, a mass proportion of the chelating agent is 0.01% to 20%, a mass proportion of the etching additive is 0.01% to 20%, a mass proportion of the fluorides is 0.01% to 20%, a mass proportion of the stabilizer is 0.01% to 5%, and a mass proportion of water is to allow a total mass proportion of the etching solution composition to be 100%.
  • In the etching solution composition according to one embodiment of the present invention, the hydrogen peroxide is served as a main oxidant of the Cu/Mo metal or Cu/Mo alloy. Preferably, the mass proportion of the hydrogen peroxide in the etching solution composition is 4% to 25%. When the mass proportion of the hydrogen peroxide is less than 4%, the acidification of the Cu/Mo alloy will be insufficient, so that the etching cannot be executed. When the mass proportion of the hydrogen peroxide exceeds 25%, the etching speed will be so fast, such that it is difficult to control the progress of the process.
  • In the etching solution composition according to one embodiment of the present invention, the etching inhibitor can adjust the etching speed of Cu/Mo metal or Cu/Mo alloy to allow them to form the etching profile with appropriate taper angles. Preferably, the mass proportion of the etching inhibitor is 6% to 10%. When the mass proportion of the etching inhibitor is less than 6%, the performance of adjusting the taper angles will be reduced. When the mass proportion of the etching inhibitor exceeds 10%, the etching speed will slow down, and then the engineering efficiency is affected.
  • Furthermore, in the etching solution composition according to one embodiment of the present invention, the etching inhibitor can be one or more of a heterocyclic aromatic compound, a heterocyclic aliphatic compound, an aromatic polyol, an ammonia monohydrate, quinoline, and a linear polyol; and the stabilizer is one or more of ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, ethanol, and isopropanol. Specifically, the heterocyclic aromatic compound can be furan, thiophene, pyrrole, oxazole, thiazole, pyrazole, triazole, tetrazole, benzofuran, benzothiophene, indole, benzothiazole, benzoimidazole, benzopyrazole, aminotetrazole, or methyl. The heterocyclic aliphatic compound can be piperazine, methyl piperazine, pyrrolidine, or alloxan. The aromatic polyol can be gallic acid, methyl ester, ethyl ester, propanol salt, or butyl ester. The linear polyol can be polyol from glycerol, erythritol, sorbitol, mannitol, or xylitol.
  • In the etching solution composition according to one embodiment of the present invention, the chelating agent forms chelation with the copper and molybdenum ions generated during etching and deactivates them, so as to inhibit the decomposition of hydrogen peroxide in the etching solution. If the chelating agent is not added into the etching solution composition of the present invention, the metallic ions which are acidized cannot be deactivated during etching. The acidized metallic ions can facilitate decomposition of the hydrogen peroxide in the etching solution composition and cause heat and explosion. Preferably, the mass proportion of the chelating agent in the etching solution composition is 0.01% to 20%, and the mass proportion of the chelating agent in the etching solution composition is more preferably 6% to 20%. If the mass proportion of the chelating agent is less than 0.01%, amount of the metallic ions to be deactivated is very few, and thus the performance of inhibiting the decomposition of the hydrogen peroxide will be reduced. If the mass proportion of the chelating agent exceeds 20%, the excess chelation is formed, and then the effect of deactivation of the metallic ions is poor and the engineering efficiency is affected.
  • Furthermore, in the etching solution composition according to one embodiment of the present invention, the chelating agent can be one or more of iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylene triamine pentaacetic acid, methylene phosphate, etidronic acid, ethylenediaminetetraacetic acid, diethylenetriamine, sarcosine, alanine, aminobutyric acid, glutamate, glycine, 1-diphosphonic acid, an organic polyphosphonic acid, and ethylenediaminetetraacetic acid.
  • In the etching solution composition according to one embodiment of the present invention, for the purpose of improving the etching performance, an etching additive can also be included. The etching additive can be a surfactant for promoting the etching performance. Preferably, the mass proportion of the etching additive in the etching solution composition is 0.01% to 20%; more preferably, the mass proportion of the etching additive in the etching solution composition is 6% to 20%. Specifically, the etching additive can be one or more of an organic acid, an inorganic acid, an organic acid salt, and an inorganic acid salt, wherein the organic acid can be acetic acid, formic acid, butyric acid, citric acid, glycolic acid, oxalic acid, 1,3-propanedioic acid, pentanoic acid, propionic acid, tartaric acid, gluconic acid, glycine, succinic acid, butanedioic acid, alkyl methanesulfonic acid, alkyl benzenesulfonic acid, alkyl diphenyl ether disulfonic acid, alkyl naphthalenesulfonic acid, naphthalenesulfonic acid, naphthalene disulfonic acid, polymer of formaldehyde and naphthalenesulfonic acid, polymer of acrylamide methyl propane sulfonic acid, acrylic acid, sulfonic acid group of vinyl benzenesulfonic acid polymer, or sulfonate compounds. The inorganic acid can be nitric acid, sulfuric acid, hydrochloric acid, hypochlorous acid, permanganic acid, phosphoric acid, boric acid, hyposulfurous acid, perchloric acid, permonosulfuric acid, peroxydisulfuric acid, or peroxydicarbonic acid.
  • In the etching solution composition according to one embodiment of the present invention, the fluorides can enhance the etching speed of the Mo alloy when the Cu/Mo alloy is etched simultaneously, and reduce the length of tails in order to remove the residue of the Mo alloy generated during etching. If the tail of the Mo alloy increases, it will reduce the brightness. The residues remaining on the substrate and the lower film will cause electrical short-circuiting, poor wiring, and reduced brightness. Therefore, the residues must be removed. Preferably, the mass proportion of the fluorides in the etching solution composition is 0.01% to 20%, and more preferably, the mass proportion of the fluorides is 6% to 20%. When the mass proportion of the fluorides is less than 0.01%, the residues of the Mo alloy cannot be removed efficiently. When the mass proportion of the fluorides exceeds 20%, the lower film will be etched.
  • Furthermore, the fluorides according to one embodiment of the present invention are compounds which dissociate fluoride ions, which can be hafnium fluoride, sodium fluoride, potassium fluoride, aluminum fluoride, fluoroboric acid, ammonium fluoride, ammonium hydrogen difluoride, sodium bifluoride, potassium bifluoride, or ammonium fluoroborate. It is also possible to use one or more of the above fluorides at the same time.
  • In the etching solution composition according to one embodiment of the present invention, the stabilizer is to control the decomposition of the hydrogen peroxide when the etching process is repeated and the content of the metallic ions in the etching solution is high. Amines can inhibit the decomposition of the hydrogen peroxide caused by the increased concentration of the metallic ions in the etching process, and have the effect of maintaining the etching properties for a long period of time. The etching stabilizer used in the present invention has larger hydrophilicity and has the effect for inhibiting the formation of the metallic residue. Preferably, the mass proportion of the stabilizer in the etching solution composition is 0.01% to 5%, and more preferably, the mass proportion of the stabilizer is 3% to 50%.
  • Furthermore, the stabilizer can be one or more of ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, ethanol, and isopropanol.
  • The etching solution composition of the present invention can be used for etching the Cu/Mo alloy film of electrodes of TFT-LCD display or OLED. When etching the Cu/Mo film or the Cu/Mo alloy film, and when the etching process is repeated, even the concentration of the metallic ions in the etching solution is increased, the metallic ions can be stabilized to control the decomposition of the hydrogen peroxide and increase the number of etching cycles and etching capacity, as well as maintain the etching properties such as etching taper angles, the etching deviation, and the etching straightness, so that the amount of the etching solution used in the etching process can be reduced and then the producing cost of TFT-LCD and OLED can be reduced significantly.
  • In summary, the present invention has been described with preferred embodiments as disclosed above, but the above preferred embodiments are not intend to limit the present invention. It is understood that many changes and modifications to the described embodiments can be carried out by the skilled person in the art without departing from the scope and the spirit of the invention that is intended to be limited only by the appended claims.

Claims (18)

What is claimed is:
1. An etching solution composition, comprising: hydrogen peroxide, an etching inhibitor, a chelating agent, an etching additive, fluorides, a stabilizer, and water;
wherein, in the etching solution composition, a mass proportion of the hydrogen peroxide is 4% to 25%, a mass proportion of the etching inhibitor is 6% to 10%, a mass proportion of the chelating agent is 0.01% to 20%, a mass proportion of the etching additive is 0.01% to 20%, a mass proportion of the fluorides is 0.01% to 20%, a mass proportion of the stabilizer is 0.01% to 5%, and a mass proportion of water is to allow a total mass proportion of the etching solution composition to be 100%;
wherein the etching inhibitor is one or more of a heterocyclic aromatic compound, a heterocyclic aliphatic compound, an aromatic polyol, an ammonia monohydrate, quinoline, and a linear polyol; and the stabilizer is one or more of ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, ethanol, and isopropanol.
2. The etching solution composition according to claim 1, wherein the mass proportion of the chelating agent in the etching solution composition is 6% to 20%.
3. The etching solution composition according to claim 1, wherein the mass proportion of the etching additive in the etching solution composition is 6% to 20%.
4. The etching solution composition according to claim 1, wherein the mass proportion of the fluorides in the etching solution composition is 6% to 20%.
5. The etching solution composition according to claim 1, wherein the mass proportion of the stabilizer in the etching solution composition is 3% to 50%.
6. The etching solution composition according to claim 1, wherein the etching additive is one or more of an organic acid, an inorganic acid, an organic acid salt, and an inorganic acid salt.
7. The etching solution composition according to claim 1, wherein the chelating agent is one or more of iminodiacetic acid, nitrilotriacetic acid, ethylenediamine tetraacetic acid, diethylene triamine pentaacetic acid, methylene phosphate, aetidronic acid, ethylenediamine tetraacetic acid, diethylenetriamine, sarcosine, alanine, aminobutyric acid, glutamate, glycine, 1-diphosphonic acid, an organic polyphosphonic acid, and ethylenediamine tetraacetic acid.
8. The etching solution composition according to claim 1, wherein the fluorides are compounds which dissociate fluoride ions.
9. An etching solution composition, comprising: hydrogen peroxide, an etching inhibitor, a chelating agent, an etching additive, fluorides, a stabilizer, and water;
wherein, in the etching solution composition, a mass proportion of the hydrogen peroxide is 4% to 25%, a mass proportion of the etching inhibitor is 6% to 10%, a mass proportion of the chelating agent is 0.01% to 20%, a mass proportion of the etching additive is 0.01% to 20%, a mass proportion of the fluorides is 0.01% to 20%, a mass proportion of the stabilizer is 0.01% to 5%, and a mass proportion of water is to allow a total mass proportion of the etching solution composition to be 100%.
10. The etching solution composition according to claim 9, wherein the mass proportion of the chelating agent in the etching solution composition is 6% to 20%.
11. The etching solution composition according to claim 9, wherein the mass proportion of the etching additive in the etching solution composition is 6% to 20%.
12. The etching solution composition according to claim 9, wherein the mass proportion of the fluorides in the etching solution composition is 6% to 20%.
13. The etching solution composition according to claim 9, wherein the mass proportion of the stabilizer in the etching solution composition is 3% to 50%.
14. The etching solution composition according to claim 9, wherein the etching inhibitor is one or more of a heterocyclic aromatic compound, a heterocyclic aliphatic compound, an aromatic polyol, an ammonia monohydrate, quinoline, and a linear polyol.
15. The etching solution composition according to claim 9, wherein the etching additive is an organic acid, and inorganic acid, and organic acid salt, and an inorganic acid salt.
16. The etching solution composition according to claim 9, wherein the chelating agent is one or more of iminodiacetic acid, nitrilotriacetic acid, ethylenediamine tetraacetic acid, diethylene triamine pentaacetic acid, methylene phosphate, etidronic acid, ethylenediamine tetraacetic acid, diethylenetriamine, sarcosine, alanine, aminobutyric acid, glutamate, glycine, 1-diphosphonic acid, an organic polyphosphonic acid, and ethylenediamine tetraacetic acid.
17. The etching solution composition according to claim 9, the stabilizer is one or more of ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, ethanol, and isopropanol.
18. The etching solution composition according to claim 9, wherein the fluorides are compounds which dissociate fluoride ions.
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