WO2018070837A1 - Etching solution composition - Google Patents

Etching solution composition Download PDF

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Publication number
WO2018070837A1
WO2018070837A1 PCT/KR2017/011332 KR2017011332W WO2018070837A1 WO 2018070837 A1 WO2018070837 A1 WO 2018070837A1 KR 2017011332 W KR2017011332 W KR 2017011332W WO 2018070837 A1 WO2018070837 A1 WO 2018070837A1
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Prior art keywords
acid
etching
weight
parts
copper
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PCT/KR2017/011332
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French (fr)
Korean (ko)
Inventor
이명한
안호원
김세훈
Original Assignee
주식회사 이엔에프테크놀로지
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Priority to CN201780002827.8A priority Critical patent/CN108235710B/en
Publication of WO2018070837A1 publication Critical patent/WO2018070837A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/10—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a boron compound
    • 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

Definitions

  • the present invention relates to an etchant composition.
  • it relates to an etchant composition used as an electrode of a TFT-LCD display.
  • a process of forming a metal wiring on a substrate is generally required by a sputtering process for forming a metal film, a photoresist forming process of a desired pattern by photoresist coating, exposure and development, an etching process for forming a wiring, and after wiring formation. It consists of a stripping process to remove the missing photoresist.
  • Aluminum or aluminum alloy layers are commonly used as wiring materials for gates and data line electrodes of thin film transistors (TFTs) to manufacture substrates of semiconductor devices and TFT-LCDs.
  • TFTs thin film transistors
  • the process of using a copper film for wiring formation has a problem in that adhesive strength with a silicon insulating film is inferior. Titanium, molybdenum, titanium / molybdenum alloys, etc. are used as the lower barrier metal film to compensate for the disadvantages of the copper film.
  • the barrier metal is a titanium / molybdenum alloy
  • etching is performed only under specific ions or under specific conditions due to the chemical nature of titanium.
  • the etching process is advantageous when the barrier metal is molybdenum, but has a disadvantage in that adhesion between the copper film and the molybdenum film is lower than that of the copper / titanium and copper / molybdenum alloy films.
  • the over-etching phenomenon due to the penetration of the etchant is intensified in the portion where the adhesion between the copper film and the molybdenum film is poor.
  • Korean Patent No. 10-1495619 discloses a hydrogen peroxide-based etching solution.
  • the etching solution is an etching solution for the molybdenum alloy film, and thus, in the case of the copper / molybdenum alloy film, the interface protection is not considered for the portion where the adhesion between copper and the barrier film is inferior, thereby causing an overetching problem at the interface of the copper / molybdenum film.
  • the cyclic amine compound binds to copper ions generated during etching of the copper film. In this case, when chlorine ions are present in the etching composition, when chlorine ions and the combination react, a poorly soluble precipitate is generated. Have.
  • An object of the present invention is to provide an etching solution composition which has excellent and stable etching performance by controlling overetching at an interface between copper and molybdenum films during etching of copper and molybdenum films, and can improve etching characteristics.
  • the present invention to achieve the above object is hydrogen peroxide; Cyclic or aromatic compounds containing any one or two or more selected from oxygen, sulfur and nitrogen in the molecule; Aminocarboxylic or amino phosphate compounds; Any one or two or more compounds selected from organic acids, inorganic acids or salts thereof; Undercut inhibitors; And it relates to an etchant composition comprising an alkylamine comprising C 4 or more.
  • the etchant composition according to an embodiment of the present invention is based on 100 parts by weight of hydrogen peroxide, 0.1 to 50 parts by weight of a cyclic or aromatic compound; 0.1 to 50 parts by weight of an aminocarboxyl or aminophosphate compound; 0.1 to 50 parts by weight of any one or two or more compounds selected from organic acids, inorganic acids or salts thereof; 0.01 to 20 parts by weight of an undercut inhibitor; And 0.1 to 50 parts by weight of alkylamine.
  • the etchant composition according to an embodiment of the present invention may further include a fluorine compound.
  • the fluorine compound according to an embodiment of the present invention may be added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of hydrogen peroxide.
  • the alkylamine including the C 4 or more may be a linear or branched alkylamine compound including C 4 to C 16 .
  • Alkylamine containing at least C 4 is any one or a mixture of two or more selected from butylamine, pentylamine, hexylamine, heptylamine, octylamine and 2-ethyl-1-hexylamine Can be.
  • the cyclic or aromatic compound according to an embodiment of the present invention is oxazole, imidazole, pyrazole, triazole, tetrazole, 5-aminotetrazole, methyltetrazole, piperazine, methylpiperazine, hydroxylethyl pipepe It may be any one or a mixture of two or more selected from razin, benzimidazole, benzpyrazole, tolutriazole, hydrotolutriazole and hydroxytolutriazole.
  • the aminocarboxyl-based or aminophosphate-based compound according to an embodiment of the present invention may include a carboxylic acid group or a phosphonic acid group together with an intramolecular amino group.
  • the aminocarboxylic or aminophosphoric acid compound according to an embodiment of the present invention is iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetrinitrilepentaacetic acid, aminotris (methylenephosphonic acid), (1- Hydroxyethane-1,1-diyl) bis (phosphonic acid), ethylenediamine tetra (methylenephosphonic acid), diethylenetriamine penta (methylenephosphonic acid), alanine, glutamic acid, aminobutyric acid and glycine, or the like It may be a mixture of two or more.
  • the inorganic acid according to an embodiment of the present invention may be any one or a mixture of two or more selected from sulfuric acid, nitric acid and phosphoric acid,
  • the organic acid may be any one or a mixture of two or more selected from acetic acid, formic acid, butanoic acid, citric acid, glycolic acid, oxalic acid, malonic acid, pentanic acid, propionic acid, tartaric acid, gluconic acid, glycoic acid and succinic acid,
  • the inorganic acid salt and the organic acid salt may be any one or a mixture of two or more selected from potassium hydrogen phosphate, sodium hydrogen phosphate, ammonium hydrogen phosphate, sodium phosphate, sodium perphosphate, potassium phosphate, potassium perphosphate, ammonium phosphate, and ammonium perphosphate.
  • the fluorine compound according to an embodiment of the present invention is HF, NaF, KF, AlF 3 , HBF, NH 4 HF 2 , NaHF 2 , KHF 2 And NH 4 BF 4 , or a mixture of two or more thereof.
  • the undercut inhibitor according to an embodiment of the present invention may be one or a mixture of two or more selected from adenine, guanine, isoguanine, hypoxanthine, xanthine, theobromine, caffeine, and urinic acid.
  • the etchant composition according to an embodiment of the present invention may further include any one or two or more additives selected from an over-water stabilizer, an etchant, and a glass etchant.
  • the etchant composition according to the present invention may control overetching of the copper and molybdenum film interfaces, increase stability of the etching composition, and enable an excellent and stable etching process.
  • the etchant composition of the present invention protects the interface during the etching process as compared to the conventional etchant composition, can improve the etching characteristics such as tapered angle, CDi Ross and visual linearity, there is an effective advantage in reducing the defective rate.
  • FIG. 1 is a photograph observed by a scanning electron microscope by tilting a cross section of a specimen after etching a copper and molybdenum film using an etchant composition according to Example 1 of the present invention.
  • FIG. 2 is a photograph of the copper and molybdenum films etched using the etchant composition according to Example 6 and then observed by scanning electron microscopy by tilting the cross section of the specimen.
  • FIG. 3 is a photograph of the copper and molybdenum films etched using the etchant composition according to Example 11 and then observed by scanning electron microscopy by tilting the cross section of the specimen.
  • Figure 6 is a photograph of the cross-section of the specimen after etching the copper and molybdenum film using the etchant composition according to Example 1 of the present invention with a scanning electron microscope.
  • Figure 7 is a photograph of the cross-section of the specimen after etching the copper / molybdenum film using the etchant composition according to Comparative Example 6 of the present invention with a scanning electron microscope.
  • the present invention is hydrogen peroxide; Cyclic or aromatic compounds containing any one or two or more selected from oxygen, sulfur and nitrogen in the molecule; Aminocarboxylic or amino phosphate compounds; Any one or two or more compounds selected from organic acids, inorganic acids or salts thereof; Undercut inhibitors; And it relates to an etchant composition comprising an alkylamine comprising C 4 or more.
  • the etchant composition is hydrogen peroxide; Cyclic or aromatic compounds containing any one or two or more selected from oxygen, sulfur and nitrogen in the molecule; Aminocarboxylic or amino phosphate compounds; Any one or two or more compounds selected from organic acids, inorganic acids or salts thereof; Undercut inhibitors; And by including all of the alkylamine containing C 4 or more it is possible to effectively etch the copper and molybdenum film at the same time.
  • the over-etching of the copper and molybdenum film interface can be suppressed, and the over-etching phenomenon due to etching liquid penetration can be effectively controlled at the portion where the adhesion between the copper and molybdenum film is poor.
  • it is possible to perform a stable etching process through the control of the over-etching phenomenon it has the characteristics that can significantly improve the etching characteristics by protecting the interface between the copper and molybdenum film
  • copper and molybdenum film means a copper film and a molybdenum film, and may exclude copper films and molybdenum alloy films other than the copper film and molybdenum film.
  • the adhesion between the copper film and the barrier film is superior to the copper and molybdenum film, and may not be considered an alkylamine containing C 4 or more.
  • the etchant composition according to an embodiment of the present invention is based on 100 parts by weight of hydrogen peroxide, 0.1 to 50 parts by weight of a cyclic or aromatic compound; 0.1 to 50 parts by weight of an aminocarboxyl or aminophosphate compound; 0.1 to 50 parts by weight of any one or two or more compounds selected from organic acids, inorganic acids or salts thereof; 0.01 to 20 parts by weight of an undercut inhibitor; And 0.1 to 50 parts by weight of alkylamine. Within this range, the over-etching control effect of the copper and molybdenum film interfaces is excellent.
  • the etchant composition according to one embodiment of the present invention is based on 100 parts by weight of hydrogen peroxide, 1 to 20 parts by weight of a cyclic or aromatic compound; 1 to 20 parts by weight of an aminocarboxyl or aminophosphate compound; 1 to 20 parts by weight of any one or two or more compounds selected from organic acids, inorganic acids or salts thereof; 0.1 to 20 parts by weight of an undercut inhibitor; And 1 to 20 parts by weight of alkylamine.
  • the over-etching of the copper and molybdenum film interfaces can be more effectively controlled, and the etching characteristics such as taper angle, CD-ROS, and visual straightness can be effectively improved.
  • the etchant composition according to an embodiment of the present invention based on 100 parts by weight of hydrogen peroxide, 2 to 10 parts by weight of a cyclic or aromatic compound; 5 to 15 parts by weight of an aminocarboxyl or aminophosphate compound; 1 to 10 parts by weight of any one or two or more compounds selected from organic acids, inorganic acids or salts thereof; 1 to 5 parts by weight of an undercut inhibitor; And 1 to 10 parts by weight of alkylamine.
  • the over-etching control effect of the copper and molybdenum film interfaces can be remarkably improved, and the etching characteristics such as excellent taper angle, sidore and visual straightness can be secured.
  • Hydrogen peroxide according to an embodiment of the present invention may act as a main oxidizing agent of copper and molybdenum, or copper and molybdenum films.
  • Hydrogen peroxide according to an embodiment of the present invention may include 10 to 30% by weight, preferably 15 to 25% by weight based on the etching liquid composition.
  • the hydrogen peroxide is included in less than 10% by weight, the etching may not be performed because the oxidizing power of copper and molybdenum is not enough, and when the hydrogen peroxide is included in excess of 30% by weight may be difficult to control the process is too fast.
  • the hydrogen peroxide can implement the desired etching rate to prevent the etching residue and the etching failure.
  • CD loss may be reduced and process control may be easier.
  • the cyclic or aromatic compound including any one or two or more selected from oxygen, sulfur and nitrogen in the molecule controls the etching rate of copper and molybdenum, thereby reducing the CD loss of the pattern. Can be reduced.
  • a cyclic or aromatic compound including any one or two or more selected from oxygen, sulfur, and nitrogen in the molecule may increase the margin of the process and allow an etch profile having an appropriate taper angle.
  • the cyclic or aromatic compound containing any one or two or more selected from oxygen, sulfur and nitrogen in the molecule may be oxazole, imidazole, pyrazole, triazole. ), Tetrazole, 5-aminotetrazole, methyltetrazole, piperazine, methylpiperazine, hydroxylethylpiperazine, hydroxyethylpiperazine, benzimi Bezimidazole, benzpyrazole, tolutriazole, hydrotolutriazole, and hydroxytolutriazole, or a mixture of two or more thereof, This is not restrictive.
  • the cyclic or aromatic compound including any one or two or more selected from oxygen, sulfur and nitrogen in the molecule of the present invention based on 100 parts by weight of hydrogen peroxide, 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, even better It may be preferable to include 2 to 10 parts by weight.
  • a cyclic or aromatic compound including any one or two or more selected from oxygen, sulfur and nitrogen within the above range may be preferable because it can maintain an appropriate etching rate.
  • the etching rate may be reduced and inefficient.
  • the aminocarboxyl-based or aminophosphate-based compound according to an embodiment of the present invention forms chelates with metal ions such as copper ions and molybdenum ions generated during etching to prevent side reactions caused by these metals. can do. As a result, the etching characteristics can be maintained even in the repeated etching process.
  • the copper layer when a large amount of copper ions remain in the etching solution composition, a passivation film is formed and oxidized to prevent etching.
  • the amino carboxyl or amino phosphate compound when added, Passivation film formation can be prevented.
  • the aminocarboxyl-based or aminophosphate-based compound may increase the stability of the etchant by preventing the decomposition reaction of hydrogen peroxide itself.
  • the oxidized metal ions are activated during the etching process so that the etching characteristics of the etchant are easily changed, and the decomposition reaction of hydrogen peroxide is promoted. Explosion may occur.
  • the aminocarboxyl-based or amino-phosphate-based compound of the present invention inhibits decomposition of hydrogen peroxide by chelation with metal ions generated during an etching process, and may play a role of increasing stability even when the etching composition is stored. have.
  • the aminocarboxyl-based or aminophosphate-based compound according to an embodiment of the present invention may include a carboxylic acid group or a phosphonic acid group together with an amino group in the molecule.
  • the aminocarboxyl-based or aminophosphate-based compound may be iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, or diethylenetrinitrilepentaacetic acid.
  • the aminocarboxyl-based or aminophosphate-based compound may be preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, even more preferably 5 to 15 parts by weight based on 100 parts by weight of hydrogen peroxide. It may be desirable to deactivate the metal ions with excellent efficiency within the above range, and to prevent side reactions to the metal ions.
  • the amount of metal ions that can be deactivated may be so small that the ability to control the hydrogen peroxide decomposition reaction may be reduced, and when included in excess of 50 parts by weight, additional chelate formation may occur. As it can not be expected to deactivate the metal can be inefficient.
  • Any one or two or more compounds selected from organic acids, inorganic acids or salts thereof in accordance with one embodiment of the present invention can serve as auxiliary oxidizers for copper and molybdenum and improve the data profile.
  • the inorganic acid may be any one or a mixture of two or more selected from sulfuric acid, nitric acid and phosphoric acid, but is not limited thereto.
  • the organic acid may be any one or a mixture of two or more selected from acetic acid, formic acid, butanoic acid, citric acid, glycolic acid, oxalic acid, malonic acid, pentanic acid, propionic acid, tartaric acid, gluconic acid, glycoic acid and succinic acid, etc. This is not restrictive.
  • the salts thereof, the inorganic acid salts and the organic acid salts may be phosphates, potassium hydrogen phosphate, sodium hydrogen phosphate, ammonium hydrogen phosphate, or phosphoric acid. Any one or a mixture of two or more selected from sodium phosphate, sodium perphosphate, potassium phosphate, potassium perphosphate, ammonium phosphate and ammonium perphosphate And, preferably ammonium hydrogen phosphate (ammonium hydrogen phosphate) may be preferable because of the excellent effect of improving the etching characteristics, but is not limited thereto.
  • Any one or two or more compounds selected from the organic acids, inorganic acids or salts thereof preferably contain 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, even more preferably 1 to 10 parts by weight based on 100 parts by weight of hydrogen peroxide. can do.
  • the taper profile improvement effect according to the use of any one or two or more compounds selected from organic acids, inorganic acids or salts thereof may be excellent, and the lowering of the etching characteristics may be suppressed.
  • the content of the cyclic or aromatic compound including any one or two or more selected from oxygen, sulfur, and nitrogen in the molecule can be controlled.
  • the content of the fluorine compound is reduced, there may be a residue of molybdenum, and when the content of a cyclic or aromatic compound including any one or two or more selected from oxygen, sulfur, and nitrogen in the molecule is increased, the copper may be etched. The speed can be significantly reduced, making the etching process difficult to progress.
  • the present invention includes an undercut inhibitor, thereby preventing the occurrence of residues of the molybdenum film and a decrease in the etching rate of copper.
  • the undercut inhibitor according to an embodiment of the present invention may be a compound including any one or more functional groups selected from the group consisting of amino groups, hydroxy groups, carbonyl groups and methyl groups in the condensation structure of pyrimidine and imidazole.
  • the undercut inhibitor includes at least one functional group selected from the group consisting of amino groups, hydroxy groups, carbonyl groups and methyl groups in the condensation structure of pyrimidine and imidazole, thereby exhibiting excellent adsorption properties to molybdenum, resulting in a large undercut inhibitory effect and excellent Etch characteristics can be improved.
  • the undercut inhibitors are adenine, guanine, isoguanine, hypoxanthine, xanthine, theobromine, caffeine, and uric acid. acid) and one or two or more mixtures thereof may be purine bases, and adenine, guanine, and isoguanine may be preferred, but are not limited thereto.
  • the undercut inhibitor may include 0.01 to 20 parts by weight, more preferably 0.1 to 20 parts by weight, 1 to 5 parts by weight based on 100 parts by weight of hydrogen peroxide. Within the above range, the improvement effect according to the use of the undercut inhibitor is excellent, and the etching rate may not be reduced and may be preferable.
  • the etching solution may be penetrated into a portion in which the adhesive strength is decreased during the etching process.
  • the defect rate may increase due to a taper angle defect due to overetching at the interface between the copper film and the molybdenum film, and a short circuit of the wiring.
  • an alkylamine containing C 4 or more by controlling the over-etching of the copper film and molybdenum film interface to improve the etching profile, it can be effective in reducing the defective rate.
  • the alkylamine containing C 4 or more may be a linear or branched alkylamine compound including C 4 to C 16 , preferably C 4 to C 8 . Since it can selectively adsorb
  • the alkylamine containing C 4 or more is butylamine, pentylamine, hexylamine, hexylamine, heptylamine, octylamine, and 2-ethyl-1- It may be any one or a mixture of two or more selected from hexylamine (2-Ethyl-1-hexylamine).
  • the alkylamine containing C 4 or more may include 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, and even more preferably 1 to 10 parts by weight based on 100 parts by weight of hydrogen peroxide.
  • the over-etching control effect of the interface according to the interface protection may be very excellent.
  • it does not cause the residue of molybdenum, there is no electrical short and wiring defects due to the residue, and may be preferable because it does not reduce the brightness.
  • the etchant composition may further include a fluorine compound.
  • the fluorine compound may improve the etching rate of the molybdenum film to reduce tail length, and may remove the molybdenum residue that is inevitably generated during etching. Increasing the tail of molybdenum may reduce the brightness, and it may be desirable to remove it since the residue will remain on the substrate and underlayer, reducing electrical shorts, wiring defects and brightness.
  • the fluorine compound according to an embodiment of the present invention may be used a compound capable of dissociating to generate F ⁇ or HF 2 ⁇ .
  • the fluorine compound is HF, NaF, KF, AlF 3 , HBF, NH 4 HF 2 , NaHF 2 , KHF 2 And NH 4 BF 4 It may be any one or a mixture of two or more selected from, but is not limited thereto.
  • the fluorine compound may be added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of hydrogen peroxide. Within the above range, the residue of molybdenum can be effectively removed, and lower layer etching such as glass substrate can be suppressed.
  • the etchant composition of the present invention may further include water, and the water contained in the etchant composition is not particularly limited, but deionized water may be preferable.
  • the water may be more preferably deionized water having a specific resistance of 18 M ⁇ / cm or more, which is a degree of removing ions in water.
  • the water may be added in an amount of 200 to 1,000 parts by weight, more preferably 250 to 800 parts by weight, and more preferably 300 to 500 parts by weight, based on 100 parts by weight of hydrogen peroxide.
  • the etchant composition according to an embodiment of the present invention may further include any additives commonly used in the etchant composition to improve the etching performance.
  • the additive may further include any one or two or more additives selected from an overwater stabilizer, an etch stabilizer and a glass etch inhibitor.
  • the perwater stabilizer may function to control the hydrogen peroxide decomposition reaction when the metal ion content in the etching solution is high by repeating the etching process.
  • the perwater stabilizer may be any one or a mixture of two or more selected from phosphates, glycols and amines. Specifically, it may include polyethylene glycol, and the like, but is not limited thereto.
  • the perwater stabilizer When the perwater stabilizer is included in the etchant composition, it may be added in an amount of 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, and more preferably 5 to 15 parts by weight, based on 100 parts by weight of hydrogen peroxide. have. Within the above range, the perwater stabilizer may be preferable because it has an excellent control effect on the hydrogen peroxide decomposition reaction and does not lower the etching ability.
  • the etching stabilizer may be a compound having an alcohol group and an amine group at the same time.
  • one or a mixture of two or more selected from methanolamine, ethanolamine, propanolamine, butanolamine, diethanolamine, triethanolamine, dimethylethanolamine, and N-methylethanolamine may be used.
  • the etching stabilizer may be added in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 7 parts by weight, and more preferably 0.1 to 5 parts by weight based on 100 parts by weight of hydrogen peroxide. Within the above range, the etching stabilizer can effectively suppress the generation of metal residues.
  • the glass etching inhibitor may be a mixture of any one or more selected from boric acid or borate. As a specific example, it may be any one or a mixture of two or more selected from HBF 4 , NaBF 4 , KBF 4 and NH 4 BF 4 , but is not limited thereto.
  • the glass etching inhibitor may be added in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 7 parts by weight, and more preferably 0.1 to 5 parts by weight based on 100 parts by weight of hydrogen peroxide. Within the above range, the glass etching inhibitory effect is excellent, and the etching rate may not be reduced, and thus may be preferable.
  • the etchant composition of the present invention having the above-mentioned composition protects the interface between the copper film and the molybdenum film during etching of the copper and molybdenum films, thereby controlling the occurrence of overetching of the interface to enable a stable etching process.
  • etching characteristics such as taper angle, CD loss, and visual linearity can be improved.
  • the etching rate can be easily adjusted.
  • the etchant composition is useful as an etchant composition for forming a metal wiring pattern when a copper and molybdenum film is used as a metal wiring material for a gate, source, or drain electrode constituting a thin film transistor (TFT) of a liquid crystal display.
  • TFT thin film transistor
  • the copper and molybdenum film according to an embodiment of the present invention may be a multilayer film in which at least one copper film (Cu) and at least one molybdenum (Mo) film are stacked on each other, and the multilayer film may be a copper (Cu) / molybdenum (Mo) double film and the like. It may include, but is not limited to, a triple layer of copper (Cu) / molybdenum (Mo) / copper (Cu) or molybdenum (Mo) / copper (Cu) / molybdenum (Mo). The order of the film can be appropriately adjusted according to the material of the substrate, the adhesion.
  • the etching method of the copper and molybdenum film using the etchant composition according to an embodiment of the present invention may be performed according to a conventional method.
  • Etching the copper and molybdenum films on which the patterned photoresist film is formed using the etching solution composition of the present invention is not particularly limited.
  • the etching method may include forming a semiconductor structure between the substrate and the copper and molybdenum film, that is, between the substrate and the copper film or between the substrate and the molybdenum film.
  • the semiconductor structure may be a semiconductor structure for a display device such as a liquid crystal display and a plasma display panel.
  • the semiconductor structure may include at least one layer selected from a dielectric film, a conductor film, and a silicon film such as amorphous or polycrystalline.
  • the semiconductor structure can be manufactured according to a conventional method.
  • Each component was mixed with the component content (wt%) described in Table 1 below to prepare an etching solution composition according to the present invention.
  • 5-aminotetrazole was used as a cyclic or aromatic compound including any one or two or more selected from oxygen, sulfur, and nitrogen in a molecule, and is designated as ATZ.
  • Iminodiacetic acid was used as an aminocarboxyl-based or aminophosphate-based compound, and is represented by IDA.
  • Ammonium hydrogen phosphate was used as one or two or more compounds selected from organic acids, inorganic acids or salts thereof, and is designated as AHP.
  • Alkyl amines containing C 4 or more include butylamine, pentylamine, hexylamine, heptylamine, octylamine and ethyl-1-hexylamine (2-Ethyl- 1-hexylamine) was used.
  • Butylamine is b-AM
  • pentylamine is pn-AM
  • hexylamine is hex-AM
  • heptylamine is hp-AM
  • octylamine is o-AM
  • 2-ethyl -1-hexylamine is designated as 2-e-1-hx-A.
  • propylamine, ethylamine and cyclohexylamine were used as alkylamines, propylamine as pr-AM, ethylamine as e-AM, and cyclohexylamine as cyhx-AM. Notation is shown.
  • a 5500 mm thick copper film and molybdenum film were sequentially deposited on a glass substrate to prepare a specimen.
  • the specimen was subjected to a photolithography process to form a patterned resist film, and the copper and molybdenum films were etched using the etching solution compositions of Examples 1 to 29 and Comparative Examples 1 to 13, respectively.
  • the etching process was carried out for 120 seconds at 32 °C using a sprayable equipment (Mini-etcher ME-001).
  • the etching endpoint was measured.
  • the etching characteristics of the etched copper and molybdenum films such as CD loss, taper angle or over-etching of the copper and molybdenum film interfaces were observed using a scanning electron microscope (Hitachi, S-4800). .
  • the presence of copper and molybdenum film interface overetching was confirmed by scanning the microscope by tilting the specimen. The results are shown in Table 2 below.
  • Table 2 is a table showing the etching performance evaluation.
  • the etching composition of Examples 1 to 29 according to the present invention includes an alkylamine containing C 4 or more, compared to the etching solution composition of Comparative Examples 1 to 13, etch bias, CDi Ross Excellent results were obtained in both (CD loss) and taper angle.
  • Comparative Examples 1 to 7 include C 3 propylamine, it can be seen that it does not play a role of inhibiting the etching liquid penetration into the copper film and molybdenum film interface, and as a result it can be confirmed that there is over-etching.
  • Comparative Example 8 can be confirmed that there is over-etching including ethylamine, which is C 2 .
  • Comparative Example 9 does not include 5-aminotechazole (ATZ), which is a cyclic or aromatic compound including any one or two or more selected from oxygen, sulfur, and nitrogen in the molecule, so that the etching rate is difficult to control and the taper shape is poor. You can see that. Comparative Example 10 does not include the imino diacetic acid (IDA) of the amino carboxyl or amino phosphate compound, it can be seen that the over-etching occurred due to the poor control of the hydrogen peroxide decomposition reaction. Comparative Example 11 does not include ammonium hydrogen phosphate (AHP), which is one or two or more compounds selected from organic acids, inorganic acids, or salts thereof, and thus, the taper angle value is high.
  • AHP ammonium hydrogen phosphate
  • Comparative Example 12 does not contain guanine, which is an undercut inhibitor, so that molybdenum residue occurs and the taper angle value is high.
  • Comparative Example 13 includes a cyclohexylamine which is a cyclic amine compound, and it can be confirmed that overetching has not occurred because the overetch inhibition is not controlled.
  • 1 is an example 1
  • 2 is an example 6
  • 3 is an etching liquid composition according to Example 11 after etching the copper and molybdenum film and then tilted the fragments of the specimen observed from the side with a scanning electron microscope One picture is shown.
  • Figure 5 shows a photograph of the copper and molybdenum film using the etching solution composition according to Comparative Example 6 and then observed by a scanning electron microscope to tilt the cross section of the specimen.
  • FIG. 6 illustrates a photograph of a specimen obtained by etching a copper and molybdenum film using an etchant composition according to Example 1, followed by scanning electron microscopy, and FIG. 7 using an etchant composition according to Comparative Example 6; After etching the molybdenum film, a cross-sectional view of the specimen was shown by scanning electron microscopy.
  • the etching liquid composition according to the present invention enables a stable etching process by controlling overetching of the copper and molybdenum film interfaces when etching the copper and molybdenum films.
  • the results improve the etching characteristics such as taper angle, CD loss and visual straightness.

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Abstract

The present invention relates to an etching solution composition comprising: hydrogen peroxide; a cyclic or aromatic compound including in a molecule, any one or more selected from among oxygen, sulfur, and nitrogen; an amino carboxylic-based or amino phosphate-based compound; one or more compounds selected from among organic acids, inorganic acids, or salts thereof; an undercut inhibitor; and alkylamine including C4 or higher. The etching solution composition of the present invention controls over-etching at the interface between copper and molybdenum films during an etching process. Thus, the etching process is stable, and etching properties can be improved.

Description

식각액 조성물Etch solution composition
본 발명은 식각액 조성물에 관한 것이다. 특히, TFT-LCD 디스플레이의 전극으로 사용되는 식각액 조성물에 관한 것이다.The present invention relates to an etchant composition. In particular, it relates to an etchant composition used as an electrode of a TFT-LCD display.
반도체 장치에서 기판 위에 금속 배선을 형성하는 과정은 일반적으로 금속 막을 형성하기 위한 스퍼터링 공정, 포토레지스트 도포, 노광 및 현상에 의하여 원하는 패턴의 포토레지스트 형성 공정 및 배선 형성을 위한 식각 공정, 배선 형성 후 필요 없는 포토레지스트를 제거하는 박리 공정으로 이루어진다.In the semiconductor device, a process of forming a metal wiring on a substrate is generally required by a sputtering process for forming a metal film, a photoresist forming process of a desired pattern by photoresist coating, exposure and development, an etching process for forming a wiring, and after wiring formation. It consists of a stripping process to remove the missing photoresist.
반도체 장치 및 TFT-LCD의 기판을 제조하기 위해 TFT(Thin Film Transistor)의 게이트와 데이터 라인 전극용 배선 재료로 알루미늄 또는 알루미늄 합금층이 흔히 사용되었다. 하지만, 대형 디스플레이 구현을 위해서는 전극용 배선의 저항 감소가 필수적이다. 이를 위하여 저항이 낮은 금속인 구리를 배선 형성에 사용하고자 하는 시도가 진행되고 있다.Aluminum or aluminum alloy layers are commonly used as wiring materials for gates and data line electrodes of thin film transistors (TFTs) to manufacture substrates of semiconductor devices and TFT-LCDs. However, in order to realize a large display, it is necessary to reduce the resistance of the wiring for the electrode. To this end, attempts have been made to use copper, which is a metal with low resistance, in the formation of wirings.
그러나, 배선 형성을 위하여 구리 막을 이용하는 공정은 실리콘 절연 막과의 접착력이 떨어지는 문제점이 있다. 이러한 구리 막의 단점을 보완하기 위해 티타늄, 몰리브덴, 티타늄/몰리브덴 합금 등을 하부 배리어 금속막으로 사용하고 있다.However, the process of using a copper film for wiring formation has a problem in that adhesive strength with a silicon insulating film is inferior. Titanium, molybdenum, titanium / molybdenum alloys, etc. are used as the lower barrier metal film to compensate for the disadvantages of the copper film.
배리어 금속이 티타늄/몰리브덴 합금인 경우 티타늄의 화학적 성질로 인해 특정 이온 또는 특정 조건으로만 식각을 해야되는 단점이 있다. 배리어 금속이 몰리브덴인 경우 식각 공정은 유리하나, 구리/티타늄, 구리/몰리브덴 합금막에 비해 구리막과 몰리브덴 막과의 접착력이 떨어지는 단점을 가지고 있다. 특히, 구리막과 몰리브덴 막의 접착력이 떨어지는 부분에 식각액의 침투에 의한 과식각 현상이 심화된다.When the barrier metal is a titanium / molybdenum alloy, there is a disadvantage in that etching is performed only under specific ions or under specific conditions due to the chemical nature of titanium. The etching process is advantageous when the barrier metal is molybdenum, but has a disadvantage in that adhesion between the copper film and the molybdenum film is lower than that of the copper / titanium and copper / molybdenum alloy films. In particular, the over-etching phenomenon due to the penetration of the etchant is intensified in the portion where the adhesion between the copper film and the molybdenum film is poor.
구리막과 몰리브덴 합금막에 사용가능한 식각액 조성물에 관하여 대한민국 등록특허 10-1495619에는 과산화수소계 식각액이 개시되어 있다. 그러나, 상기 식각액은 몰리브덴 합금막에 대한 식각액으로 구리/몰리브덴 합금막의 경우 구리와 배리어 막간의 접착력이 떨어지는 부분에 대한 계면 보호가 고려되지 않아 구리/몰리브덴 막의 계면에 과식각 문제점이 있다. 또한, 특히 고리형 아민 화합물은 구리막 식각시 발생되는 구리 이온과 결합하는데, 이 경우 식각 조성물내에 염소 이온이 존재할 경우 염소 이온과 상기 결합물이 반응하면 난용성의 석출물이 발생하는 등의 문제점을 가지고 있다.Regarding the etching liquid composition usable for the copper film and the molybdenum alloy film, Korean Patent No. 10-1495619 discloses a hydrogen peroxide-based etching solution. However, the etching solution is an etching solution for the molybdenum alloy film, and thus, in the case of the copper / molybdenum alloy film, the interface protection is not considered for the portion where the adhesion between copper and the barrier film is inferior, thereby causing an overetching problem at the interface of the copper / molybdenum film. In addition, in particular, the cyclic amine compound binds to copper ions generated during etching of the copper film. In this case, when chlorine ions are present in the etching composition, when chlorine ions and the combination react, a poorly soluble precipitate is generated. Have.
따라서, 구리 및 몰리브덴 막의 낮은 접착력에 의해 발생하는 계면의 과식각 문제점을 개선할 수 있는 기술이 필요한 실정이다.Therefore, there is a need for a technology capable of improving the overetching problem of the interface caused by the low adhesion of copper and molybdenum films.
본 발명은 구리 및 몰리브덴 막의 식각시 구리 및 몰리브덴 막의 계면에 과식각을 제어하여 우수하고 안정적인 식각 성능을 가지며, 식각 특성을 개선시킬 수 있는 식각액 조성물을 제공하고자 한다.An object of the present invention is to provide an etching solution composition which has excellent and stable etching performance by controlling overetching at an interface between copper and molybdenum films during etching of copper and molybdenum films, and can improve etching characteristics.
상기의 목적을 달성하기 위해 본 발명은 과산화수소; 분자 내에 산소, 황 및 질소 중에서 선택되는 어느 하나 또는 둘 이상을 포함하는 환형 또는 방향족화합물; 아미노카르복실계 또는 아미노인산계화합물; 유기산, 무기산 또는 그들의 염에서 선택되는 어느 하나 또는 둘 이상의 화합물; 언더컷억제제; 및 C4 이상을 포함하는 알킬아민을 포함하는 식각액 조성물에 관한 것이다.The present invention to achieve the above object is hydrogen peroxide; Cyclic or aromatic compounds containing any one or two or more selected from oxygen, sulfur and nitrogen in the molecule; Aminocarboxylic or amino phosphate compounds; Any one or two or more compounds selected from organic acids, inorganic acids or salts thereof; Undercut inhibitors; And it relates to an etchant composition comprising an alkylamine comprising C 4 or more.
본 발명의 일 실시예에 따른 상기 식각액 조성물은 과산화수소 100 중량부를 기준으로, 환형 또는 방향족 화합물 0.1 내지 50 중량부; 아미노카르복실계 또는 아미노인산계화합물 0.1 내지 50 중량부; 유기산, 무기산 또는 그들의 염에서 선택되는 어느 하나 또는 둘 이상의 화합물 0.1 내지 50 중량부; 언터컷억제제 0.01 내지 20 중량부; 및 알킬아민 0.1 내지 50 중량부를 포함할 수 있다.The etchant composition according to an embodiment of the present invention is based on 100 parts by weight of hydrogen peroxide, 0.1 to 50 parts by weight of a cyclic or aromatic compound; 0.1 to 50 parts by weight of an aminocarboxyl or aminophosphate compound; 0.1 to 50 parts by weight of any one or two or more compounds selected from organic acids, inorganic acids or salts thereof; 0.01 to 20 parts by weight of an undercut inhibitor; And 0.1 to 50 parts by weight of alkylamine.
본 발명의 일 실시예에 따른 상기 식각액 조성물은 불소화합물을 더 포함할 수 있다.The etchant composition according to an embodiment of the present invention may further include a fluorine compound.
본 발명의 일 실시예에 따른 상기 불소화합물은 과산화수소 100 중량부를 기준으로, 0.01 내지 20 중량부로 첨가될 수 있다.The fluorine compound according to an embodiment of the present invention may be added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of hydrogen peroxide.
본 발명의 일 실시예에 따른 상기 C4 이상을 포함하는 알킬아민은 C4 내지 C16을 포함하는 직쇄형 또는 분지쇄형의 알킬아민 화합물일 수 있다.The alkylamine including the C 4 or more according to an embodiment of the present invention may be a linear or branched alkylamine compound including C 4 to C 16 .
본 발명의 일 실시예에 따른 상기 C4 이상을 포함하는 알킬아민은 부틸아민, 펜틸아민, 헥실아민, 헵틸아민, 옥틸아민 및 2-에틸-1-헥실아민에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있다.Alkylamine containing at least C 4 according to an embodiment of the present invention is any one or a mixture of two or more selected from butylamine, pentylamine, hexylamine, heptylamine, octylamine and 2-ethyl-1-hexylamine Can be.
본 발명의 일 실시예에 따른 상기 환형 또는 방향족화합물은 옥사졸, 이미다졸, 피라졸, 트리아졸, 테트라졸, 5-아미노테트라졸, 메틸테트라졸, 피페라진, 메틸피페라진, 히드록실에틸피페라진, 벤즈이미다졸, 벤즈피라졸, 톨루트리아졸, 히드로톨루트리아졸 및 히드록시톨루트리아졸에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있다.The cyclic or aromatic compound according to an embodiment of the present invention is oxazole, imidazole, pyrazole, triazole, tetrazole, 5-aminotetrazole, methyltetrazole, piperazine, methylpiperazine, hydroxylethyl pipepe It may be any one or a mixture of two or more selected from razin, benzimidazole, benzpyrazole, tolutriazole, hydrotolutriazole and hydroxytolutriazole.
본 발명의 일 실시예에 따른 상기 아미노카르복실계 또는 아미노인산계 화합물은 분자내 아미노기와 함께, 카르복실산기 또는 포스폰산기를 포함할 수 있다.The aminocarboxyl-based or aminophosphate-based compound according to an embodiment of the present invention may include a carboxylic acid group or a phosphonic acid group together with an intramolecular amino group.
본 발명의 일 실시예에 따른 상기 아미노카르복실계 또는 아미노인산계화합물은 이미노디아세트산, 니트릴로트리아세트산, 에틸렌디아민테트라아세트산, 디에틸렌트리니트릴펜타아세트산, 아미노트리스(메틸렌포스폰산), (1-히드록시에탄-1,1-디일)비스(포스폰산), 에틸렌디아민 테트라(메틸렌포스폰산), 디에틸렌트리아민 펜타(메틸렌포스폰산), 알라닌, 글루탐산, 아미노부티르산 및 글리신 등에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있다.The aminocarboxylic or aminophosphoric acid compound according to an embodiment of the present invention is iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetrinitrilepentaacetic acid, aminotris (methylenephosphonic acid), (1- Hydroxyethane-1,1-diyl) bis (phosphonic acid), ethylenediamine tetra (methylenephosphonic acid), diethylenetriamine penta (methylenephosphonic acid), alanine, glutamic acid, aminobutyric acid and glycine, or the like It may be a mixture of two or more.
본 발명의 일 실시예에 따른 상기 무기산은 황산, 질산 및 인산에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있으며,The inorganic acid according to an embodiment of the present invention may be any one or a mixture of two or more selected from sulfuric acid, nitric acid and phosphoric acid,
상기 유기산은 아세트산, 포름산, 부탄산, 시트르산, 글리콜산, 옥살산, 말론산, 펜탄산, 프로피온산, 타르타르산, 글루콘산, 글리코산 및 숙신산 등에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있으며,The organic acid may be any one or a mixture of two or more selected from acetic acid, formic acid, butanoic acid, citric acid, glycolic acid, oxalic acid, malonic acid, pentanic acid, propionic acid, tartaric acid, gluconic acid, glycoic acid and succinic acid,
상기 무기산염 및 유기산염은 인산수소칼륨, 인산수소나트륨, 인산수소암모늄, 인산나트륨, 과인산나트륨, 인산칼륨, 과인산칼륨, 인산암모늄 및 과인산암모늄 등에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있다.The inorganic acid salt and the organic acid salt may be any one or a mixture of two or more selected from potassium hydrogen phosphate, sodium hydrogen phosphate, ammonium hydrogen phosphate, sodium phosphate, sodium perphosphate, potassium phosphate, potassium perphosphate, ammonium phosphate, and ammonium perphosphate.
본 발명의 일 실시예에 따른 상기 불소화합물은 HF, NaF, KF, AlF3 , HBF, NH4HF2, NaHF2, KHF2 및 NH4BF4에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있다.The fluorine compound according to an embodiment of the present invention is HF, NaF, KF, AlF 3 , HBF, NH 4 HF 2 , NaHF 2 , KHF 2 And NH 4 BF 4 , or a mixture of two or more thereof.
본 발명의 일 실시예에 따른 상기 언더컷 억제제는 아데닌, 구아닌, 이소구아닌, 하이포크산틴, 크산틴, 테오브로민, 카페인 및 유린산 등에서 선택되는 하나 또는 둘 이상의 혼합물일 수 있다.The undercut inhibitor according to an embodiment of the present invention may be one or a mixture of two or more selected from adenine, guanine, isoguanine, hypoxanthine, xanthine, theobromine, caffeine, and urinic acid.
본 발명의 일 실시예에 따른 상기 식각액 조성물은 과수안정제, 식각안정제 및 글라스 식각억제제에서 선택되는 어느 하나 또는 둘 이상의 첨가제를 더 포함할 수 있다.The etchant composition according to an embodiment of the present invention may further include any one or two or more additives selected from an over-water stabilizer, an etchant, and a glass etchant.
본 발명에 따른 식각액 조성물은 구리 및 몰리브덴막 계면의 과식각을 제어하고, 식각 조성물의 안정성을 높여, 우수하고 안정적인 식각 공정을 가능하게 할 수 있다.The etchant composition according to the present invention may control overetching of the copper and molybdenum film interfaces, increase stability of the etching composition, and enable an excellent and stable etching process.
또한, 본 발명의 식각액 조성물은 종래의 식각액 조성물과 대비하여 식각공정시 계면을 보호하여, 테이퍼 앵글, 시디 로스 및 시각 직선성 등의 식각 특성을 개선시킬 수 있으며, 불량률 감소에 효과적인 장점이 있다.In addition, the etchant composition of the present invention protects the interface during the etching process as compared to the conventional etchant composition, can improve the etching characteristics such as tapered angle, CDi Ross and visual linearity, there is an effective advantage in reducing the defective rate.
도 1은 본 발명의 실시예 1에 따른 식각액 조성물을 이용하여 구리 및 몰리브덴 막을 식각한 후의 시편의 단면을 틸트(tilt)하여 주사전자현미경으로 관찰한 사진이다.FIG. 1 is a photograph observed by a scanning electron microscope by tilting a cross section of a specimen after etching a copper and molybdenum film using an etchant composition according to Example 1 of the present invention.
도 2는 본 발명의 실시예 6에 따른 식각액 조성물을 이용하여 구리 및 몰리브덴 막을 식각한 후 시편의 단면을 틸트(tilt)하여 주사전자현미경으로 관찰한 사진이다.FIG. 2 is a photograph of the copper and molybdenum films etched using the etchant composition according to Example 6 and then observed by scanning electron microscopy by tilting the cross section of the specimen.
도 3은 본 발명의 실시예 11에 따른 식각액 조성물을 이용하여 구리 및 몰리브덴 막을 식각한 후 시편의 단면을 틸트(tilt)하여 주사전자현미경으로 관찰한 사진이다.FIG. 3 is a photograph of the copper and molybdenum films etched using the etchant composition according to Example 11 and then observed by scanning electron microscopy by tilting the cross section of the specimen.
도 4는 본 발명의 비교예 1에 따른 식각액 조성물을 이용하여 구리 및 몰리브덴 막을 식각한 후 시편의 단면을 틸트(tilt)하여 주사전자현미경으로 관찰한 사진이다.4 is a photograph of the copper and molybdenum films etched using the etchant composition according to Comparative Example 1 of the present invention and then observed by scanning electron microscopy by tilting the cross section of the specimen.
도 5는 본 발명의 비교예 6에 따른 식각액 조성물을 이용하여 구리 및 몰리브덴 막을 식각한 후 시편의 단면을 틸트(tilt)하여 주사전자현미경으로 관찰한 사진이다.5 is a photograph of the copper and molybdenum films etched using the etchant composition according to Comparative Example 6 of the present invention and then observed by scanning electron microscopy by tilting the cross section of the specimen.
도 6은 본 발명의 실시예 1에 따른 식각액 조성물을 이용하여 구리 및 몰리브덴 막을 식각한 후 시편의 단면을 주사전자현미경으로 관찰한 사진이다.Figure 6 is a photograph of the cross-section of the specimen after etching the copper and molybdenum film using the etchant composition according to Example 1 of the present invention with a scanning electron microscope.
도 7은 본 발명의 비교예 6에 따른 식각액 조성물을 이용하여 구리/몰리브덴 막을 식각한 후 시편의 단면을 주사전자현미경으로 관찰한 사진이다.Figure 7 is a photograph of the cross-section of the specimen after etching the copper / molybdenum film using the etchant composition according to Comparative Example 6 of the present invention with a scanning electron microscope.
이하, 본 발명의 실시예에 따른 식각액 조성물에 대하여 보다 상세하게 설명한다.Hereinafter, the etching liquid composition according to an embodiment of the present invention will be described in more detail.
본 발명은 과산화수소; 분자 내에 산소, 황 및 질소 중에서 선택되는 어느 하나 또는 둘 이상을 포함하는 환형 또는 방향족화합물; 아미노카르복실계 또는 아미노인산계화합물; 유기산, 무기산 또는 그들의 염에서 선택되는 어느 하나 또는 둘 이상의 화합물; 언더컷억제제; 및 C4 이상을 포함하는 알킬아민을 포함하는 식각액 조성물에 관한 것이다.The present invention is hydrogen peroxide; Cyclic or aromatic compounds containing any one or two or more selected from oxygen, sulfur and nitrogen in the molecule; Aminocarboxylic or amino phosphate compounds; Any one or two or more compounds selected from organic acids, inorganic acids or salts thereof; Undercut inhibitors; And it relates to an etchant composition comprising an alkylamine comprising C 4 or more.
상기 식각액 조성물은 과산화수소; 분자 내에 산소, 황 및 질소 중에서 선택되는 어느 하나 또는 둘 이상을 포함하는 환형 또는 방향족화합물; 아미노카르복실계 또는 아미노인산계화합물; 유기산, 무기산 또는 그들의 염에서 선택되는 어느 하나 또는 둘 이상의 화합물; 언더컷억제제; 및 C4 이상을 포함하는 알킬아민을 모두 포함함으로써 구리 및 몰리브덴 막을 동시에 효과적으로 식각할 수 있다. 또한, 구리 및 몰리브덴 막 계면의 과식각을 억제할 수 있어, 구리 및 몰리브덴 막의 접착력이 떨어지는 부분에 식각액 침투에 의한 과식각 현상을 효과적으로 제어할 수 있다. 또한, 과식각 현상의 제어를 통해 안정적인 식각 공정을 수행할 수 있고, 구리 및 몰리브덴 막의 계면을 보호해 식각 특성을 현저하게 개선할 수 있는 특징이 있다The etchant composition is hydrogen peroxide; Cyclic or aromatic compounds containing any one or two or more selected from oxygen, sulfur and nitrogen in the molecule; Aminocarboxylic or amino phosphate compounds; Any one or two or more compounds selected from organic acids, inorganic acids or salts thereof; Undercut inhibitors; And by including all of the alkylamine containing C 4 or more it is possible to effectively etch the copper and molybdenum film at the same time. In addition, the over-etching of the copper and molybdenum film interface can be suppressed, and the over-etching phenomenon due to etching liquid penetration can be effectively controlled at the portion where the adhesion between the copper and molybdenum film is poor. In addition, it is possible to perform a stable etching process through the control of the over-etching phenomenon, it has the characteristics that can significantly improve the etching characteristics by protecting the interface between the copper and molybdenum film
본 발명에서 "구리 및 몰리브덴 막"이란, 구리막과 몰리브덴막을 의미하며, 구리막과 몰리브덴막 이외의 구리막과 몰리브덴 합금막을 제외할 수 있다. In the present invention, "copper and molybdenum film" means a copper film and a molybdenum film, and may exclude copper films and molybdenum alloy films other than the copper film and molybdenum film.
상기 몰리브덴 합금막의 경우, 구리 및 몰리브덴 막보다 구리 막과 배리어 막간의 접착력이 우수하여, C4 이상을 포함하는 알킬아민의 고려 대상이 아닐 수 있다.In the case of the molybdenum alloy film, the adhesion between the copper film and the barrier film is superior to the copper and molybdenum film, and may not be considered an alkylamine containing C 4 or more.
본 발명의 일 실시예에 따른 상기 식각액 조성물은 과산화수소 100 중량부를 기준으로, 환형 또는 방향족 화합물 0.1 내지 50 중량부; 아미노카르복실계 또는 아미노인산계화합물 0.1 내지 50 중량부; 유기산, 무기산 또는 그들의 염에서 선택되는 어느 하나 또는 둘 이상의 화합물 0.1 내지 50 중량부; 언터컷억제제 0.01 내지 20 중량부; 및 알킬아민 0.1 내지 50 중량부를 포함할 수 있다. 이와 같은 범위에서 구리 및 몰리브덴막 계면의 과식각 제어 효과가 뛰어나다.The etchant composition according to an embodiment of the present invention is based on 100 parts by weight of hydrogen peroxide, 0.1 to 50 parts by weight of a cyclic or aromatic compound; 0.1 to 50 parts by weight of an aminocarboxyl or aminophosphate compound; 0.1 to 50 parts by weight of any one or two or more compounds selected from organic acids, inorganic acids or salts thereof; 0.01 to 20 parts by weight of an undercut inhibitor; And 0.1 to 50 parts by weight of alkylamine. Within this range, the over-etching control effect of the copper and molybdenum film interfaces is excellent.
보다 좋게는, 본 발명의 일 예에 따른 식각액 조성물은 과산화수소 100 중량부를 기준으로, 환형 또는 방향족 화합물 1 내지 20 중량부; 아미노카르복실계 또는 아미노인산계화합물 1 내지 20 중량부; 유기산, 무기산 또는 그들의 염에서 선택되는 어느 하나 또는 둘 이상의 화합물 1 내지 20 중량부; 언터컷억제제 0.1 내지 20 중량부; 및 알킬아민 1 내지 20 중량부를 포함할 수 있다. 이와 같은 범위에서 구리 및 몰리브덴막 계면의 과식각을 더욱 효과적으로 제어할 수 있으며, 테이퍼 앵글, 시디 로스 및 시각 직진성 등의 식각 특성을 효과적으로 개선할 수 있다.More preferably, the etchant composition according to one embodiment of the present invention is based on 100 parts by weight of hydrogen peroxide, 1 to 20 parts by weight of a cyclic or aromatic compound; 1 to 20 parts by weight of an aminocarboxyl or aminophosphate compound; 1 to 20 parts by weight of any one or two or more compounds selected from organic acids, inorganic acids or salts thereof; 0.1 to 20 parts by weight of an undercut inhibitor; And 1 to 20 parts by weight of alkylamine. In such a range, the over-etching of the copper and molybdenum film interfaces can be more effectively controlled, and the etching characteristics such as taper angle, CD-ROS, and visual straightness can be effectively improved.
특히 바람직하게, 본 발명의 일 예에 따른 식각액 조성물은 과산화수소 100 중량부를 기준으로, 환형 또는 방향족 화합물 2 내지 10 중량부; 아미노카르복실계 또는 아미노인산계화합물 5 내지 15 중량부; 유기산, 무기산 또는 그들의 염에서 선택되는 어느 하나 또는 둘 이상의 화합물 1 내지 10 중량부; 언터컷억제제 1 내지 5 중량부; 및 알킬아민 1 내지 10 중량부를 포함할 수 있다. 이와 같은 범위에서 구리 및 몰리브덴막 계면의 과식각 제어 효과를 현저하게 향상시킬 수 있으며, 우수한 테이퍼 앵글, 시디 로스 및 시각 직진성 등의 식각 특성을 확보할 수 있다.Particularly preferably, the etchant composition according to an embodiment of the present invention, based on 100 parts by weight of hydrogen peroxide, 2 to 10 parts by weight of a cyclic or aromatic compound; 5 to 15 parts by weight of an aminocarboxyl or aminophosphate compound; 1 to 10 parts by weight of any one or two or more compounds selected from organic acids, inorganic acids or salts thereof; 1 to 5 parts by weight of an undercut inhibitor; And 1 to 10 parts by weight of alkylamine. In such a range, the over-etching control effect of the copper and molybdenum film interfaces can be remarkably improved, and the etching characteristics such as excellent taper angle, sidore and visual straightness can be secured.
이하 본 발명의 일 실시예에 따른 식각액 조성물의 각 구성성분들에 대해 보다 구체적인 일 예로 설명한다.Hereinafter, each component of the etchant composition according to an embodiment of the present invention will be described as a specific example.
a) 과산화수소a) hydrogen peroxide
본 발명의 일 실시예에 따른 과산화수소는 구리와 몰리브덴, 또는 구리 및 몰리브덴 막의 주 산화제로 작용할 수 있다.Hydrogen peroxide according to an embodiment of the present invention may act as a main oxidizing agent of copper and molybdenum, or copper and molybdenum films.
본 발명의 일 실시예에 따른 과산화수소는 식각액 조성물에 대하여 10 내지 30 중량%를 포함할 수 있으며, 좋게는 15 내지 25 중량%를 포함하는 것이 바람직할 수 있다. 상기 과산화수소가 10 중량% 미만으로 포함될 경우, 구리와 몰리브덴의 산화력이 충분하지 않아 식각이 이루어지지 않을 수 있으며, 과산화수소가 30 중량%를 초과하여 포함될 경우 식각 속도가 너무 빨라 공정 제어가 어려워질 수 있다. 상기의 범위 내에서, 과산화수소는 바람직한 식각속도를 구현할 수 있어 식각 잔사 및 식각 불량을 방지할 수 있다. 또한, 시디로스(CD loss)가 감소하고 공정 조절이 용이할 수 있다.Hydrogen peroxide according to an embodiment of the present invention may include 10 to 30% by weight, preferably 15 to 25% by weight based on the etching liquid composition. When the hydrogen peroxide is included in less than 10% by weight, the etching may not be performed because the oxidizing power of copper and molybdenum is not enough, and when the hydrogen peroxide is included in excess of 30% by weight may be difficult to control the process is too fast. . Within the above range, the hydrogen peroxide can implement the desired etching rate to prevent the etching residue and the etching failure. In addition, CD loss may be reduced and process control may be easier.
b) 분자 내에 산소, 황 및 질소 중에서 선택되는 어느 하나 또는 둘 이상을 포함하는 환형 또는 방향족화합물b) cyclic or aromatic compounds comprising one or two or more selected from oxygen, sulfur and nitrogen in the molecule
본 발명의 일 실시예에 따른 분자 내에 산소, 황 및 질소 중에서 선택되는 어느 하나 또는 둘 이상을 포함하는 환형 또는 방향족화합물은 구리 및 몰리브덴의 식각 속도를 조절하여, 패턴의 시디 로스(CD loss)를 줄여줄 수 있다. 또한, 분자 내에 산소, 황 및 질소 중에서 선택되는 어느 하나 또는 둘 이상을 포함하는 환형 또는 방향족화합물은 공정의 마진을 높이며, 적절한 테이퍼앵글을 갖는 식각 프로파일이 되도록 할 수 있는 것이다.The cyclic or aromatic compound including any one or two or more selected from oxygen, sulfur and nitrogen in the molecule according to an embodiment of the present invention controls the etching rate of copper and molybdenum, thereby reducing the CD loss of the pattern. Can be reduced. In addition, a cyclic or aromatic compound including any one or two or more selected from oxygen, sulfur, and nitrogen in the molecule may increase the margin of the process and allow an etch profile having an appropriate taper angle.
구체적인 일 예로, 상기 분자 내에 산소, 황 및 질소 중에서 선택되는 어느 하나 또는 둘 이상을 포함하는 환형 또는 방향족화합물은 옥사졸(oxazole), 이미다졸(imidazole), 피라졸(pyrazole), 트리아졸(triazole), 테트라졸(tetrazole), 5-아미노테트라졸(5-aminotetrazole), 메틸테트라졸(methyltetrazole), 피페라진(piperazine), 메틸피페라진(methylpiperazine), 히드록실에틸피페라진(hydroxyethylpiperazine), 벤즈이미다졸(benzimidazole), 벤즈피라졸(benzpyrazole), 톨루트리아졸(tolutriazole), 히드로톨루트리아졸(hydrotolutriazole) 및 히드록시톨루트리아졸(hydroxytolutriazole)에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있으며, 이에 제한되지 않는다.As a specific example, the cyclic or aromatic compound containing any one or two or more selected from oxygen, sulfur and nitrogen in the molecule may be oxazole, imidazole, pyrazole, triazole. ), Tetrazole, 5-aminotetrazole, methyltetrazole, piperazine, methylpiperazine, hydroxylethylpiperazine, hydroxyethylpiperazine, benzimi Bezimidazole, benzpyrazole, tolutriazole, hydrotolutriazole, and hydroxytolutriazole, or a mixture of two or more thereof, This is not restrictive.
본 발명의 분자 내에 산소, 황 및 질소 중에서 선택되는 어느 하나 또는 둘 이상을 포함하는 환형 또는 방향족화합물은 과산화수소 100 중량부를 기준으로, 0.1 내지 50 중량부, 보다 좋게는 1 내지 20 중량부, 더욱 좋게는 2 내지 10 중량부를 포함하는 것이 바람직할 수 있다. 상기 범위 내에서 산소, 황 및 질소 중에서 선택되는 어느 하나 또는 둘 이상을 포함하는 환형 또는 방향족화합물은 적절한 식각 속도를 유지할 수 있어 바람직할 수 있다. The cyclic or aromatic compound including any one or two or more selected from oxygen, sulfur and nitrogen in the molecule of the present invention, based on 100 parts by weight of hydrogen peroxide, 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, even better It may be preferable to include 2 to 10 parts by weight. A cyclic or aromatic compound including any one or two or more selected from oxygen, sulfur and nitrogen within the above range may be preferable because it can maintain an appropriate etching rate.
상기 분자 내에 산소, 황 및 질소 중에서 선택되는 어느 하나 또는 둘 이상을 포함하는 환형 또는 방향족화합물이 0.1 중량부 미만으로 포함될 경우 식각 속도 조절이 어렵고, 테이퍼 앵글을 조절할 수 있는 능력이 저하될 수 있으며, 공정 마진이 적어 양산성이 저하될 수 있다. 또한, 분자 내에 산소, 황 및 질소 중에서 선택되는 어느 하나 또는 둘 이상을 포함하는 환형 또는 방향족화합물이 50 중량부를 초과하여 포함되는 경우 식각 속도가 감소하여 비효율적일 수 있다.When the cyclic or aromatic compound containing any one or two or more selected from oxygen, sulfur and nitrogen in the molecule is less than 0.1 parts by weight, it is difficult to control the etching rate, and the ability to adjust the taper angle may be lowered. Low process margins may lead to lower productivity. In addition, when the cyclic or aromatic compound containing any one or two or more selected from oxygen, sulfur and nitrogen in the molecule in excess of 50 parts by weight, the etching rate may be reduced and inefficient.
c) 아미노카르복실계 또는 아미노인산계화합물c) aminocarboxylic or aminophosphate compounds
본 발명의 일 실시예에 따른 아미노카르복실계 또는 아미노인산계화합물은 식각이 진행되는 동안 발생하는 구리이온, 몰리브덴 이온 등의 금속 이온들과 킬레이트를 형성하여 비활성화 시킴으로써 이들 금속에 의한 부반응 발생을 방지할 수 있다. 그 결과 반복되는 식각 공정에도 식각 특성을 유지할 수 있도록 한다. The aminocarboxyl-based or aminophosphate-based compound according to an embodiment of the present invention forms chelates with metal ions such as copper ions and molybdenum ions generated during etching to prevent side reactions caused by these metals. can do. As a result, the etching characteristics can be maintained even in the repeated etching process.
특히 구리층의 경우, 식각액 조성물 중에 구리 이온이 다량으로 잔존할 경우 패시베이션(passivation) 막을 형성하여 산화되어, 식각이 되지 않는 문제점이 있으나, 아미노카르복실계 또는 아미노인산계화합물의 투입시 구리 이온의 패시베이션(passivation) 막 형성을 방지할 수 있다. 또한, 아미노카르복실계 또는 아미노인산계화합물은 과산화수소 자체의 분해반응을 방지하여 식각액의 안정성을 증가시킬 수 있다. Particularly, in the case of the copper layer, when a large amount of copper ions remain in the etching solution composition, a passivation film is formed and oxidized to prevent etching. However, when the amino carboxyl or amino phosphate compound is added, Passivation film formation can be prevented. In addition, the aminocarboxyl-based or aminophosphate-based compound may increase the stability of the etchant by preventing the decomposition reaction of hydrogen peroxide itself.
만약, 식각액 조성물 중에 아미노카르복실계 또는 아미노인산계화합물이 첨가되지 않을 경우, 식각이 진행되는 동안 산화된 금속 이온이 활성화되어 식각액의 식각 특성이 변화되기 쉽고, 과산화수소의 분해 반응이 촉진되어 발명 및 폭발이 발생할 수 있다.If an aminocarboxyl or amino phosphate compound is not added to the etchant composition, the oxidized metal ions are activated during the etching process so that the etching characteristics of the etchant are easily changed, and the decomposition reaction of hydrogen peroxide is promoted. Explosion may occur.
따라서, 본 발명의 아미노카르복실계 또는 아미노인산계화합물은 식각공정 시 발생되는 금속이온들과 킬레이션(chelation)하여 과산화수소의 분해를 억제하며, 식각 조성물의 보관시에도 안정성을 높이는 역할을 할 수 있다.Therefore, the aminocarboxyl-based or amino-phosphate-based compound of the present invention inhibits decomposition of hydrogen peroxide by chelation with metal ions generated during an etching process, and may play a role of increasing stability even when the etching composition is stored. have.
본 발명의 일 실시예에 따른 상기 아미노카르복실계 또는 아미노인산계화합물은 분자내 아미노기와 함께, 카르복실산기 또는 포스폰산기를 포함할 수 있다.The aminocarboxyl-based or aminophosphate-based compound according to an embodiment of the present invention may include a carboxylic acid group or a phosphonic acid group together with an amino group in the molecule.
구체적인 일 예로, 상기 아미노카르복실계 또는 아미노인산계화합물은 이미노디아세트산(iminodiacetic acid), 니트릴로트리아세트산(nitrilotriacetic acid), 에틸렌디아민테트라아세트산(ethylenediaminetetraacetic acid), 디에틸렌트리니트릴펜타아세트산(diethylenetrinitrilacetic acid), 아미노트리스(메틸렌포스폰산)aminotris(methylenephosphonic acid)), (1-히드록시에탄-1,1-디일)비스(포스폰산)((1-hydroxyethane-1,1-diyl)bis(phosphonic acid)), 에틸렌디아민 테트라(메틸렌포스폰산))(ethylenediamine tetra(methylene phosphonic acid)), 디에틸렌트리아민 펜타(메틸렌포스폰산))(Diethylenetriamine penta(methylene phosphonic acid), 알라닌(alanine), 글루탐산(glutamic acid), 아미노부티르산(aminobutyric acid) 및 글리신(glycin) 등에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있으며, 바람직하게는 이미노디아세트산(iminodiacetic acid)일 수 있으나, 이에 제한되지 않는다.As a specific example, the aminocarboxyl-based or aminophosphate-based compound may be iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, or diethylenetrinitrilepentaacetic acid. , Aminotris (methylenephosphonic acid) aminotris (methylenephosphonic acid)), (1-hydroxyethane-1,1-diyl) bis (phosphonic acid) ((1-hydroxyethane-1,1-diyl) bis (phosphonic acid) ), Ethylenediamine tetra (methylene phosphonic acid)) (ethylenediamine tetra (methylene phosphonic acid)), diethylenetriamine penta (methylene phosphonic acid)) (Diethylenetriamine penta (methylene phosphonic acid), alanine, glutamic acid ), Aminobutyric acid, glycine (glycin), and any one or a mixture of two or more, preferably iminodiacetic acid), but is not limited thereto.
상기 아미노카르복실계 또는 아미노인산계화합물은 과산화수소 100 중량부를 기준으로, 0.1 내지 50 중량부, 보다 좋게는 1 내지 20 중량부, 더욱 좋게는 5 내지 15 중량부를 포함하는 것이 바람직할 수 있다. 상기 범위 내에서 우수한 효율로 금속 이온들을 비활성화 시킬 수 있고, 금속 이온에 대한 부반응을 방지할 수 있어 바람직할 수 있다.The aminocarboxyl-based or aminophosphate-based compound may be preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, even more preferably 5 to 15 parts by weight based on 100 parts by weight of hydrogen peroxide. It may be desirable to deactivate the metal ions with excellent efficiency within the above range, and to prevent side reactions to the metal ions.
상기 아미노카르복실계 또는 아미노인산계화합물이 0.1 중량부 미만으로 포함될 경우 비활성화시킬 수 있는 금속 이온량이 너무 작아서 과산화수소 분해반응을 제어하는 능력이 떨어질 수 있고, 50 중량부을 초과하여 포함되는 경우 추가적인 킬레이트 형성으로 금속을 비활성화 시키는 작용을 기대할 수 없어 비효율적일 수 있다. When the aminocarboxyl- or aminophosphate-based compound is included in less than 0.1 part by weight, the amount of metal ions that can be deactivated may be so small that the ability to control the hydrogen peroxide decomposition reaction may be reduced, and when included in excess of 50 parts by weight, additional chelate formation may occur. As it can not be expected to deactivate the metal can be inefficient.
d) 유기산, 무기산 또는 그들의 염에서 선택되는 어느 하나 또는 둘 이상의 화합물d) any one or two or more compounds selected from organic acids, inorganic acids or salts thereof
본 발명의 일 실시예에 따른 유기산, 무기산 또는 그들의 염에서 선택되는 어느 하나 또는 둘 이상의 화합물은 구리 및 몰리브덴에 대한 보조 산화제의 역할을 하며, 테이터 프로파일을 개선시킬 수 있다.Any one or two or more compounds selected from organic acids, inorganic acids or salts thereof in accordance with one embodiment of the present invention can serve as auxiliary oxidizers for copper and molybdenum and improve the data profile.
구체적인 일 예로, 상기 무기산은 황산, 질산 및 인산 등에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있으나, 이에 제한되지 않는다.As a specific example, the inorganic acid may be any one or a mixture of two or more selected from sulfuric acid, nitric acid and phosphoric acid, but is not limited thereto.
구체적인 일 예로, 상기 유기산은 아세트산, 포름산, 부탄산, 시트르산, 글리콜산, 옥살산, 말론산, 펜탄산, 프로피온산, 타르타르산, 글루콘산, 글리코산 및 숙신산 등에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있으나, 이에 제한되지 않는다.As a specific example, the organic acid may be any one or a mixture of two or more selected from acetic acid, formic acid, butanoic acid, citric acid, glycolic acid, oxalic acid, malonic acid, pentanic acid, propionic acid, tartaric acid, gluconic acid, glycoic acid and succinic acid, etc. This is not restrictive.
구체적인 일 예로, 상기 그들의 염인, 무기산염 및 유기산염은 인산염(phosphate)일 수 있으며, 인산수소칼륨(potassium hydrogen phosphate), 인산수소나트륨(sodium hydrogen phosphate), 인산수소암모늄(ammonium hydrogen phosphate), 인산나트륨(sodium phosphate), 과인산나트륨(sodium perphosphate), 인산칼륨(potassium phosphate), 과인산칼륨(potassium perphosphate), 인산암모늄(ammonium phosphate) 및 과인산암모늄(ammonium perphosphate) 등에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있으며, 좋게는 인산수소암모늄(ammonium hydrogen phosphate)이 식각특성 개선효과가 우수하여 바람직할 수 있으나, 이에 제한되지 않는다.As a specific example, the salts thereof, the inorganic acid salts and the organic acid salts may be phosphates, potassium hydrogen phosphate, sodium hydrogen phosphate, ammonium hydrogen phosphate, or phosphoric acid. Any one or a mixture of two or more selected from sodium phosphate, sodium perphosphate, potassium phosphate, potassium perphosphate, ammonium phosphate and ammonium perphosphate And, preferably ammonium hydrogen phosphate (ammonium hydrogen phosphate) may be preferable because of the excellent effect of improving the etching characteristics, but is not limited thereto.
상기 유기산, 무기산 또는 그들의 염에서 선택되는 어느 하나 또는 둘 이상의 화합물는 과산화수소 100 중량부를 기준으로, 0.1 내지 50 중량부, 보다 좋게는 1 내지 20 중량부, 더욱 좋게는 1 내지 10 중량부를 포함하는 것이 바람직할 수 있다. 상기 범위 내에서 유기산, 무기산 또는 그들의 염에서 선택되는 어느 하나 또는 둘 이상의 화합물 사용에 따른 테이퍼 프로파일 개선 효과가 우수하고, 식각특성의 저하를 억제할 수 있어 바람직할 수 있다. Any one or two or more compounds selected from the organic acids, inorganic acids or salts thereof preferably contain 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, even more preferably 1 to 10 parts by weight based on 100 parts by weight of hydrogen peroxide. can do. Within the above range, the taper profile improvement effect according to the use of any one or two or more compounds selected from organic acids, inorganic acids or salts thereof may be excellent, and the lowering of the etching characteristics may be suppressed.
e) 언더컷 억제제e) undercut inhibitor
구리 및 몰리브덴 막의 동시 식각시 몰리브덴 막의 언더컷의 식각을 제어하기 위해서 불소화합물 및 분자 내에 산소, 황 및 질소 중에서 선택되는 어느 하나 또는 둘 이상을 포함하는 환형 또는 방향족화합물의 함량으로 조절할 수 있다. 그런데, 불소화합물의 함량을 작게 하는 경우 몰리브덴의 잔사가 발생할 우려가 있고, 분자 내에 산소, 황 및 질소 중에서 선택되는 어느 하나 또는 둘 이상을 포함하는 환형 또는 방향족화합물의 함량을 증가시키는 경우 구리의 식각속도가 현저하게 감소하여 식각 공정의 진행이 어려워질 수 있다.In order to control the etching of the undercut of the molybdenum film at the time of simultaneous etching of the copper and molybdenum film, the content of the cyclic or aromatic compound including any one or two or more selected from oxygen, sulfur, and nitrogen in the molecule can be controlled. However, when the content of the fluorine compound is reduced, there may be a residue of molybdenum, and when the content of a cyclic or aromatic compound including any one or two or more selected from oxygen, sulfur, and nitrogen in the molecule is increased, the copper may be etched. The speed can be significantly reduced, making the etching process difficult to progress.
이에 대해 본 발명은 언더컷 억제제를 포함하여, 몰리브덴 막의 잔사 발생이나 구리의식각속도 저하를 방지할 수 있다.In contrast, the present invention includes an undercut inhibitor, thereby preventing the occurrence of residues of the molybdenum film and a decrease in the etching rate of copper.
본 발명의 일 실시예에 따른 상기 언더컷 억제제는 피리미딘과 이미다졸의 축합 구조 내에 아미노기, 히드록시기, 카르보닐기 및 메틸기로 이루어진 군에서 선택되는 어느 하나 이상의 작용기를 포함하는 화합물일 수 있다.The undercut inhibitor according to an embodiment of the present invention may be a compound including any one or more functional groups selected from the group consisting of amino groups, hydroxy groups, carbonyl groups and methyl groups in the condensation structure of pyrimidine and imidazole.
상기 언더컷 억제제는 피리미딘과 이미다졸의 축합 구조 내에 아미노기, 히드록시기, 카르보닐기 및 메틸기로 이루어진 군에서 선택되는 어느 하나 이상의 작용기를 포함함으로써, 몰리브덴에 대해 우수한 흡착 특성을 나타내어, 언더컷 억제 효과가 크고, 우수한 식각 특성 개선 효과를 나타낼 수 있다.The undercut inhibitor includes at least one functional group selected from the group consisting of amino groups, hydroxy groups, carbonyl groups and methyl groups in the condensation structure of pyrimidine and imidazole, thereby exhibiting excellent adsorption properties to molybdenum, resulting in a large undercut inhibitory effect and excellent Etch characteristics can be improved.
구체적인 일 예로, 상기 언더컷 억제제는 아데닌(adenine), 구아닌(guanine), 이소구아닌(isoguanine), 하이포크산틴(hypoxanthine), 크산틴(xanthine), 테오브로민(theobromine), 카페인(caffeine) 및 유린산(uric acid) 등에서 선택되는 하나 또는 둘 이상의 혼합물인 퓨린염기(purine base)일 수 있으며, 아데닌(adenine), 구아닌(guanine) 및 이소구아닌(isoguanine)이 바람직할 수 있으나, 이에 제한되지 않는다.As a specific example, the undercut inhibitors are adenine, guanine, isoguanine, hypoxanthine, xanthine, theobromine, caffeine, and uric acid. acid) and one or two or more mixtures thereof may be purine bases, and adenine, guanine, and isoguanine may be preferred, but are not limited thereto.
상기 언더컷 억제제는 과산화수소 100 중량부를 기준으로, 0.01 내지 20 중량부, 보다 좋게는 0.1 내지 20 중량부, 1 내지 5 중량부를 포함하는 것이 바람직할 수 있다. 상기의 범위 내에서 언더컷 억제제의 사용에 따른 개선 효과가 우수하며, 식각속도가 감소되지 않아 바람직할 수 있다.The undercut inhibitor may include 0.01 to 20 parts by weight, more preferably 0.1 to 20 parts by weight, 1 to 5 parts by weight based on 100 parts by weight of hydrogen peroxide. Within the above range, the improvement effect according to the use of the undercut inhibitor is excellent, and the etching rate may not be reduced and may be preferable.
f) C4 이상을 포함하는 알킬아민f) alkylamines comprising at least C 4
구리 및 몰리브덴 막의 동시 식각시 구리막과 몰리브덴 막의 화학적 성질 때문에 접착력이 떨어지는 부분이 발생할 수 있다. 이때, 식각 공정 진행시 접착력이 떨어지는 부분에 식각액의 침투가 이루어질 수 있다. In the simultaneous etching of the copper and molybdenum film, a portion having poor adhesion due to the chemical properties of the copper film and the molybdenum film may occur. In this case, the etching solution may be penetrated into a portion in which the adhesive strength is decreased during the etching process.
이를 제어하지 못하는 경우, 구리막과 몰리브덴 막의 계면에 과식각에 의한 테이퍼 앵글 불량, 배선 단락 등 식각 프로파일 저하로 인해 불량률 증가의 원인이 될 수 있다.If this is not controlled, the defect rate may increase due to a taper angle defect due to overetching at the interface between the copper film and the molybdenum film, and a short circuit of the wiring.
이에 대해 본 발명에서는 C4 이상을 포함하는 알킬아민을 적용함으로써, 구리막과 몰리브덴 막 계면의 과식각을 제어하여 식각 프로파일을 개선시킬 수 있으며, 불량률 감소에 효과적일 수 있다.In the present invention, by applying an alkylamine containing C 4 or more, by controlling the over-etching of the copper film and molybdenum film interface to improve the etching profile, it can be effective in reducing the defective rate.
구체적으로, 상기 C4 이상을 포함하는 알킬아민은 C4 내지 C16, 좋게는 C4 내지 C8을 포함하는 직쇄형 또는 분지쇄형의 알킬아민 화합물일 수 있다. 상기의 범위 내에서 구리막과 몰리브덴 막의 접착력이 떨어지는 계면에 선택적으로 흡착할 수 있기 때문에, 식각액이 계면으로 침투하는 것을 억제하여, 구리막과 몰리브덴 막 계면의 과식각을 제어할 수 있다. 또한, C4 내지 C8를 포함하는 경우, 식각액 조성물에 거품이 발생하지 않아 더 바람직할 수 있다. 반면, 상기 알킬아민 화합물의 탄소수가 C3 이하를 가지는 경우는 식각액 침투를 억제하는 역할을 하지 못할 수 있다.Specifically, the alkylamine containing C 4 or more may be a linear or branched alkylamine compound including C 4 to C 16 , preferably C 4 to C 8 . Since it can selectively adsorb | suck to the interface with which the adhesive force of a copper film and a molybdenum film falls in the said range, it can suppress that an etching liquid penetrates into an interface, and can control overetching of an interface of a copper film and a molybdenum film. In addition, when C 4 to C 8 are included, bubbles may not be generated in the etchant composition, which may be more preferable. On the other hand, if the alkylamine compound has a carbon number of C 3 or less may not play a role in inhibiting the penetration of the etchant.
구체적인 일 예로, 상기 C4 이상을 포함하는 알킬아민은 부틸아민(butylamine), 펜틸아민(pentylamine), 헥실아민(hexylamine), 헵틸아민(heptylamine), 옥틸아민(octylamine) 및 2-에틸-1-헥실아민(2-Ethyl-1-hexylamine)에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있다.As a specific example, the alkylamine containing C 4 or more is butylamine, pentylamine, hexylamine, hexylamine, heptylamine, octylamine, and 2-ethyl-1- It may be any one or a mixture of two or more selected from hexylamine (2-Ethyl-1-hexylamine).
상기 C4 이상을 포함하는 알킬아민은 과산화수소 100 중량부를 기준으로, 0.1 내지 50 중량부, 보다 좋게는 1 내지 20 중량부, 더욱 좋게는 1 내지 10 중량부를 포함하는 것이 바람직할 수 있다. 상기 범위 내에서 계면 보호에 따른 계면의 과식각 제어 효과가 매우 우수할 수 있다. 또한, 몰리브덴의 잔사를 유발하지 않아, 잔사에 의한 전기적인 쇼트, 배선 불량이 없으며, 휘도를 감소시키지 않아 바람직할 수 있다.The alkylamine containing C 4 or more may include 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, and even more preferably 1 to 10 parts by weight based on 100 parts by weight of hydrogen peroxide. Within the above range, the over-etching control effect of the interface according to the interface protection may be very excellent. In addition, it does not cause the residue of molybdenum, there is no electrical short and wiring defects due to the residue, and may be preferable because it does not reduce the brightness.
g) 불소화합물g) fluorine compounds
본 발명에서는 식각액 조성물에 불소화합물을 더 포함할 수 있다. 불소화합물은 구리 및 몰리브덴 막을 동시에 식각할 때, 몰리브덴 막의 식각 속도를 향상시켜 테일랭스(tail length)를 감소시켜 주고, 식각시 필연적으로 발생하게 되는 몰리브덴의 잔사를 제거하는 작용을 할 수 있다. 몰리브덴의 테일 증가는 휘도를 감소시킬 수 있으며, 잔사가 기판 및 하부막에 남게 되면 전기적인 쇼트, 배선 불량 및 휘도를 감소시키므로 반드시 제거하는 것이 바람직할 수 있다.In the present invention, the etchant composition may further include a fluorine compound. When the copper and molybdenum films are simultaneously etched, the fluorine compound may improve the etching rate of the molybdenum film to reduce tail length, and may remove the molybdenum residue that is inevitably generated during etching. Increasing the tail of molybdenum may reduce the brightness, and it may be desirable to remove it since the residue will remain on the substrate and underlayer, reducing electrical shorts, wiring defects and brightness.
본 발명의 일 실시예에 따른 상기 불소화합물은 해리되어 F- 또는 HF2 -를 발생시킬 수 있는 화합물이 사용될 수 있다.The fluorine compound according to an embodiment of the present invention may be used a compound capable of dissociating to generate F − or HF 2 − .
구체적인 일 예로, 상기 불소화합물은 HF, NaF, KF, AlF3 , HBF, NH4HF2, NaHF2, KHF2 및 NH4BF4에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있으나, 이에 제한되지 않는다.As a specific example, the fluorine compound is HF, NaF, KF, AlF 3 , HBF, NH 4 HF 2 , NaHF 2 , KHF 2 And NH 4 BF 4 It may be any one or a mixture of two or more selected from, but is not limited thereto.
상기 불소화합물은 과산화수소 100 중량부를 기준으로, 0.01 내지 20 중량부로 첨가되는 것이 바람직할 수 있다. 상기의 범위 내에서 몰리브덴의 잔사를 효과적으로 제거할 수 있고, 유리기판 등의 하부막 식각을 억제할 수 있다.The fluorine compound may be added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of hydrogen peroxide. Within the above range, the residue of molybdenum can be effectively removed, and lower layer etching such as glass substrate can be suppressed.
h) 물h) water
본 발명의 식각액 조성물은 물을 더 포함할 수 있으며, 식각액 조성물에 포함되는 물은 특별히 한정되지 않으나, 탈이온수가 바람직할 수 있다. 구체적인 일 예로, 상기 물은 물 속에 이온이 제거된 정도인 비저항값이 18 ㏁/㎝ 이상인 탈이온수가 보다 바람직할 수 있다. 상기 물은 과산화수소 100 중량부를 기준으로, 200 내지 1,000 중량부로 첨가될 수 있으며, 보다 좋게는 250 내지 800 중량부, 더욱 좋게는 300 내지 500 중량부로 첨가될 수 있다.The etchant composition of the present invention may further include water, and the water contained in the etchant composition is not particularly limited, but deionized water may be preferable. As a specific example, the water may be more preferably deionized water having a specific resistance of 18 ㏁ / cm or more, which is a degree of removing ions in water. The water may be added in an amount of 200 to 1,000 parts by weight, more preferably 250 to 800 parts by weight, and more preferably 300 to 500 parts by weight, based on 100 parts by weight of hydrogen peroxide.
i) 기타 첨가제i) other additives
본 발명의 일 실시예에 따른 식각액 조성물은 식각 성능을 향상시키기 위해 통상 식각액 조성물에 사용되는 임의의 첨가제를 더 포함할 수 있다. 상기 첨가제로는 과수안정제, 식각안정제 및 글라스 식각억제제 등에서 선택되는 어느 하나 또는 둘 이상의 첨가제를 더 포함할 수 있다.The etchant composition according to an embodiment of the present invention may further include any additives commonly used in the etchant composition to improve the etching performance. The additive may further include any one or two or more additives selected from an overwater stabilizer, an etch stabilizer and a glass etch inhibitor.
상기 과수안정제는 식각 공정을 반복하여 식각액 내의 금속이온 함량이 높은 경우 과산화수소 분해 반응을 제어하는 작용을 할 수 있다.The perwater stabilizer may function to control the hydrogen peroxide decomposition reaction when the metal ion content in the etching solution is high by repeating the etching process.
구체적인 일 예로, 상기 과수안정제는 인산염, 글리콜류 및 아민류에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있다. 구체적으로, 플리에틸렌글리콜(polyethylene glycol) 등을 포함할 수 있으나, 이에 제한되지 않는다.As a specific example, the perwater stabilizer may be any one or a mixture of two or more selected from phosphates, glycols and amines. Specifically, it may include polyethylene glycol, and the like, but is not limited thereto.
상기 과수안정제가 식각액 조성물에 포함될 경우, 과산화수소 100 중량부를 기준으로, 0.1 내지 30 중량부로 첨가될 수 있으며, 보다 좋게는 1 내지 20 중량부, 더욱 좋게는 5 내지 15 중량부로 첨가되는 것이 바람직할 수 있다. 상기의 범위 내에서 과수안정제는 과산화수소 분해 반응에 대한 제어 효과가 우수하고, 식각능을 저하시키지 않아 바람직할 수 있다.When the perwater stabilizer is included in the etchant composition, it may be added in an amount of 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, and more preferably 5 to 15 parts by weight, based on 100 parts by weight of hydrogen peroxide. have. Within the above range, the perwater stabilizer may be preferable because it has an excellent control effect on the hydrogen peroxide decomposition reaction and does not lower the etching ability.
상기 식각안정제는 알코올기와 아민기를 동시에 갖는 화합물일 수 있다. 구체적인 일 예로, 메탄올아민, 에탄올아민, 프로판올아민, 부탄올아민, 디에탄올아민, 트리에탄올아민, 디메틸에탄올아민 및 N-메틸에탄올아민에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있으며, 이에 제한되지 않는다. The etching stabilizer may be a compound having an alcohol group and an amine group at the same time. As a specific example, one or a mixture of two or more selected from methanolamine, ethanolamine, propanolamine, butanolamine, diethanolamine, triethanolamine, dimethylethanolamine, and N-methylethanolamine may be used.
상기 식각안정제는 과산화수소 100 중량부를 기준으로, 0.01내지 10 중량부, 보다 좋게는 0.05 내지 7 중량부, 더욱 좋게는 0.1 내지 5 중량부로 첨가되는 것이 바람직할 수 있다. 상기의 범위 내에서 식각안정제는 금속 잔사의 발생을 효과적으로 억제할 수 있다.The etching stabilizer may be added in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 7 parts by weight, and more preferably 0.1 to 5 parts by weight based on 100 parts by weight of hydrogen peroxide. Within the above range, the etching stabilizer can effectively suppress the generation of metal residues.
상기 글라스 식각 억제제는 붕불산 또는 붕불산염에서 선택되는 어느 하나 이상의 혼합물일 수 있다. 구체적인 일 예로, HBF4, NaBF4, KBF4 및 NH4BF4 등에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있으나, 이에 제한되지 않는다.The glass etching inhibitor may be a mixture of any one or more selected from boric acid or borate. As a specific example, it may be any one or a mixture of two or more selected from HBF 4 , NaBF 4 , KBF 4 and NH 4 BF 4 , but is not limited thereto.
상기 글라스 식각 억제제의 함량은 과산화수소 100 중량부를 기준으로, 0.01내지 10 중량부, 보다 좋게는 0.05 내지 7 중량부, 더욱 좋게는 0.1 내지 5 중량부로 첨가되는 것이 바람직할 수 있다. 상기의 범위 내에서 글라스 식각 억제 효과가 우수하고, 식각 속도가 감소하지 않아 바람직할 수 있다.The glass etching inhibitor may be added in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 7 parts by weight, and more preferably 0.1 to 5 parts by weight based on 100 parts by weight of hydrogen peroxide. Within the above range, the glass etching inhibitory effect is excellent, and the etching rate may not be reduced, and thus may be preferable.
앞서 언급된 조성을 갖는 본 발명의 식각액 조성물은 구리 및 몰리브덴 막의 식각시, 구리막과 몰리브덴 막의 계면을 보호하여, 계면의 과식각 발생을 제어하여 안정적인 식각 공정을 가능하게 한다. 그 결과, 테이퍼 앵글, 시디 로스 및 시각 직선성 등의 식각 특성을 개선시킬 수 있다. 또한, 식각 속도조절이 용이할 수 있다.The etchant composition of the present invention having the above-mentioned composition protects the interface between the copper film and the molybdenum film during etching of the copper and molybdenum films, thereby controlling the occurrence of overetching of the interface to enable a stable etching process. As a result, etching characteristics such as taper angle, CD loss, and visual linearity can be improved. In addition, the etching rate can be easily adjusted.
이에 따라, 상기 식각액 조성물은 액정표시장치의 TFT(Thin Film Transistor)를 구성하는 게이트, 소스 또는 드레인 전극용 금속 배선 재료로서 구리 및 몰리브덴 막을 사용하는 경우, 금속배선 패턴을 형성하기 위한 식각액 조성물로서 유용하게 사용될 수 있다.Accordingly, the etchant composition is useful as an etchant composition for forming a metal wiring pattern when a copper and molybdenum film is used as a metal wiring material for a gate, source, or drain electrode constituting a thin film transistor (TFT) of a liquid crystal display. Can be used.
본 발명의 일 실시예에 따른 구리 및 몰리브덴 막은 하나 이상의 구리막(Cu)과 하나 이상의 몰리브덴(Mo) 막이 상호 적층된 다중막일 수 있으며, 상기 다중막은 구리(Cu)/몰리브덴(Mo) 이중막과, 구리(Cu)/몰리브덴(Mo)/구리(Cu) 또는 몰리브덴(Mo)/구리(Cu)/몰리브덴(Mo)의 삼중막을 포함할 수 있으나, 이에 제한되지 않는다. 상기 막의 순서는 기판의 물질, 접합성에 따라 적절히 조절할 수 있다.The copper and molybdenum film according to an embodiment of the present invention may be a multilayer film in which at least one copper film (Cu) and at least one molybdenum (Mo) film are stacked on each other, and the multilayer film may be a copper (Cu) / molybdenum (Mo) double film and the like. It may include, but is not limited to, a triple layer of copper (Cu) / molybdenum (Mo) / copper (Cu) or molybdenum (Mo) / copper (Cu) / molybdenum (Mo). The order of the film can be appropriately adjusted according to the material of the substrate, the adhesion.
본 발명의 일 실시예에 따른 식각액 조성물을 이용한 구리 및 몰리브덴 막의 식각방법은 통상의 방법에 따라 실시될 수 있다.The etching method of the copper and molybdenum film using the etchant composition according to an embodiment of the present invention may be performed according to a conventional method.
구체적으로, 기판 상에 구리/몰리브덴 막을 증착하는 단계; Specifically, depositing a copper / molybdenum film on the substrate;
상기 구리 및 몰리브덴 막 위에 포토레지스트 막을 형성한 후 패턴화하는 단계; 및 Forming and patterning a photoresist film on the copper and molybdenum film; And
본 발명의 식각액 조성물을 사용하여 상기 패턴화된 포토레지스트막이 형성된 구리 및 몰리브덴 막을 식각하는 단계;를 포함하는 구리 및 몰리브덴 막의 식각방법을 실시할 수 있다. 이때, 상기 기판 위에 형성되는 구리/몰리브덴 막은 그 적층순서가 특별히 한정되지 않는다.Etching the copper and molybdenum films on which the patterned photoresist film is formed using the etching solution composition of the present invention. At this time, the stacking order of the copper / molybdenum film formed on the substrate is not particularly limited.
또한, 상기 식각방법은 기판과 구리 및 몰리브덴 막 사이, 즉, 기판과 구리막 사이 또는 기판과 몰리브덴 막 사이에 반도체 구조물을 형성하는 단계를 포함할 수 있다.In addition, the etching method may include forming a semiconductor structure between the substrate and the copper and molybdenum film, that is, between the substrate and the copper film or between the substrate and the molybdenum film.
상기 반도체 구조물은 액정표시장치, 플라즈마 디스플레이 패널 등 표시장치용 반도체 구조물일 수 있다. The semiconductor structure may be a semiconductor structure for a display device such as a liquid crystal display and a plasma display panel.
구체적으로, 상기 반도체 구조물은 유전체막, 도전체막 및 비정질 또는 다결정 등의 실리콘막 중에서 선택되는 막을 1층 이상 포함할 수 있다. 상기 반도체 구조물은 통상의 방법에 따라 제조될 수 있다.Specifically, the semiconductor structure may include at least one layer selected from a dielectric film, a conductor film, and a silicon film such as amorphous or polycrystalline. The semiconductor structure can be manufactured according to a conventional method.
이하 실시예를 통한 본 발명에 따른 및 이의 제조 방법에 대하여 더욱 상세히 설명한다. 다만 하기 실시예는 본 발명을 상세히 설명하기 위한 하나의 참조일 뿐 본 발명이 이에 한정되는 것은 아니며, 여러 형태로 구현될 수 있다. Hereinafter will be described in more detail with respect to the present invention and its preparation method through the following examples. However, the following examples are only one reference for describing the present invention in detail, and the present invention is not limited thereto and may be implemented in various forms.
또한, 달리 정의되지 않는 한, 모든 기술적 용어 및 과학적 용어는 본 발명이 속하는 당업자 중 하나에 의해 일반적으로 이해되는 의미와 동일한 의미를 갖는다. 본원에서 설명에 사용되는 용어는 단지 특정 실시예를 효과적으로 기술하기 위함이고 본 발명을 제한하는 것으로 의도되지 않는다.Also, unless defined otherwise, all technical and scientific terms have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is for the purpose of effectively describing particular embodiments only and is not intended to be limiting of the invention.
또한, 다음에 소개되는 도면들은 당업자에게 본 발명의 사상이 충분히 전달될 수 있도록 하기 위해 예로서 제공되는 것이다. 따라서 본 발명은 이하 제시되는 도면들에 한정되지 않고 다른 형태로 구체화될 수도 있으며, 이하 제시되는 도면들은 본 발명의 사상을 명확히 하기 위해 과장되어 도시될 수 있다.In addition, the following drawings are provided as examples to fully convey the spirit of the present invention to those skilled in the art. Therefore, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention.
또한, 명세서 및 첨부된 특허청구범위에서 사용되는 단수 형태는 문맥에서 특별한 지시가 없는 한 복수 형태도 포함하는 것으로 의도할 수 있다.Also, the singular forms used in the specification and the appended claims may be intended to include the plural forms as well, unless the context clearly indicates otherwise.
[[ 실시예Example 1 내지 29, 및  1 to 29, and 비교예Comparative example 1 내지 13] 1 to 13]
하기 표 1에 기재된 성분 함량(중량%)으로 각 성분을 혼합하여, 본 발명에 따른 식각액 조성물을 준비하였다.Each component was mixed with the component content (wt%) described in Table 1 below to prepare an etching solution composition according to the present invention.
중량(%)weight(%)
과산화수소Hydrogen peroxide AATZAATZ IDAIDA AHPAHP NH4HF2 NH 4 HF 2 구아닌Guanine C4 이상을 포함하는 알킬아민Alkylamine containing at least C 4 물water
실시예1Example 1 1515 1One 22 1One 0.50.5 0.50.5 b-AMb-AM 1.01.0 79.079.0
실시예2Example 2 1818 1One 22 1One 0.50.5 1.01.0 b-AMb-AM 1.01.0 75.575.5
실시예3Example 3 2020 1One 22 1One 0.50.5 0.50.5 b-AMb-AM 1.01.0 74.074.0
실시예4Example 4 2020 1One 22 1One 0.50.5 1.01.0 b-AMb-AM 1.51.5 73.073.0
실시예5Example 5 2020 1One 22 1One -- 1.01.0 b-AMb-AM 1.51.5 73.573.5
실시예6Example 6 1818 1One 22 1One 0.50.5 1.01.0 pn-AMpn-AM 1.01.0 75.575.5
실시예7Example 7 1818 1One 22 1One -- 1.01.0 pn-AMpn-AM 1.01.0 76.076.0
실시예8Example 8 2020 1One 22 1One 0.50.5 0.50.5 pn-AMpn-AM 1.01.0 74.074.0
실시예9Example 9 1818 1One 22 1One 0.50.5 1.01.0 pn-AMpn-AM 1.51.5 75.075.0
실시예10Example 10 2020 1One 22 1One 0.50.5 0.50.5 pn-AMpn-AM 1.51.5 73.573.5
실시예11Example 11 1818 1One 22 1One 0.50.5 1.01.0 hx-AMhx-AM 1.01.0 75.575.5
실시예12Example 12 1818 1One 22 1One -- 1.01.0 hx-AMhx-AM 1.01.0 76.076.0
실시예13Example 13 2020 1One 22 1One 0.50.5 0.50.5 hx-AMhx-AM 1.01.0 74.074.0
실시예14Example 14 1818 1One 22 1One 0.50.5 1.01.0 hx-AMhx-AM 1.51.5 75.075.0
실시예15Example 15 2020 1One 22 1One 0.50.5 0.50.5 hx-AMhx-AM 1.51.5 73.573.5
실시예16Example 16 1515 1One 22 1One 0.50.5 0.50.5 hp-AMhp-AM 1.01.0 79.079.0
실시예17Example 17 1818 1One 22 1One 0.50.5 0.50.5 hp-AMhp-AM 1.01.0 76.076.0
실시예18Example 18 2020 1One 22 1One 0.50.5 0.50.5 hp-AMhp-AM 1.01.0 74.074.0
실시예19Example 19 1818 1One 22 1One -- 0.50.5 hp-AMhp-AM 1.51.5 76.076.0
실시예20Example 20 2020 1One 22 1One 0.50.5 0.50.5 hp-AMhp-AM 1.51.5 73.573.5
실시예21Example 21 1515 1One 22 1One 0.50.5 0.50.5 o-AMo-AM 1.01.0 79.079.0
실시예22Example 22 2020 1One 22 1One 0.50.5 1.01.0 o-AMo-AM 1.01.0 73.573.5
실시예23Example 23 2020 1One 22 1One -- 0.50.5 o-AMo-AM 1.01.0 74.574.5
실시예24Example 24 1818 1One 22 1One 0.50.5 1.01.0 o-AMo-AM 1.51.5 75.075.0
실시예25Example 25 2020 1One 22 1One 0.50.5 0.50.5 o-AMo-AM 1.51.5 73.573.5
실시예26Example 26 1818 1One 22 1One 0.50.5 0.50.5 2-e-1-hx-A2-e-1-hx-A 1.01.0 76.076.0
실시예27Example 27 2020 1One 22 1One 0.50.5 1.01.0 2-e-1-hx-A2-e-1-hx-A 1.01.0 73.573.5
실시예28Example 28 1818 1One 22 1One 0.50.5 0.50.5 2-e-1-hx-A2-e-1-hx-A 1.51.5 75.575.5
실시예29Example 29 2020 1One 22 1One 0.50.5 1.01.0 2-e-1-hx-A2-e-1-hx-A 1.51.5 73.073.0
비교예1Comparative Example 1 1515 1One 22 1One 0.50.5 0.50.5 pr-AMpr-AM 1.01.0 79.079.0
비교예2Comparative Example 2 1818 1One 22 1One 0.50.5 1.01.0 pr-AMpr-AM 1.01.0 75.575.5
비교예3Comparative Example 3 2020 1One 22 1One 0.50.5 0.50.5 pr-AMpr-AM 1.01.0 74.074.0
비교예4Comparative Example 4 1818 1One 22 1One -- 1.01.0 pr-AMpr-AM 1.51.5 75.575.5
비교예5Comparative Example 5 2020 1One 22 1One 0.50.5 0.50.5 e-AMe-AM 1.51.5 73.573.5
비교예6Comparative Example 6 1818 1One 22 1One 0.50.5 0.50.5 -- -- 77.077.0
비교예7Comparative Example 7 1818 1One 22 1One -- 0.50.5 -- -- 77.577.5
비교예8Comparative Example 8 2020 1One 22 1One 0.50.5 1.01.0 -- -- 74.574.5
비교예9Comparative Example 9 2020 -- 22 1One 0.50.5 0.50.5 b-AMb-AM 1.01.0 75.075.0
비교예10Comparative Example 10 2020 1One -- 1One 0.50.5 0.50.5 b-AMb-AM 1.01.0 76.076.0
비교예11Comparative Example 11 2020 1One 22 -- 0.50.5 0.50.5 b-AMb-AM 1.01.0 75.075.0
비교예12Comparative Example 12 2020 1One 22 1One 0.50.5 -- b-AMb-AM 1.01.0 74.574.5
비교예13Comparative Example 13 2020 1One 22 1One 0.50.5 1.01.0 cyhx-AMcyhx-AM 1.01.0 73.573.5
상기 표 1에 나타낸 성분은 다음과 같다.The components shown in Table 1 are as follows.
분자 내에 산소, 황 및 질소 중에서 선택되는 어느 하나 또는 둘 이상을 포함하는 환형 또는 방향족화합물로 5-아미노테트라졸(5-aminotetrazole)을 사용하였으며, ATZ로 표기하였다. 5-aminotetrazole was used as a cyclic or aromatic compound including any one or two or more selected from oxygen, sulfur, and nitrogen in a molecule, and is designated as ATZ.
아미노카르복실계 또는 아미노인산계화합물로 이미노디아세트산(iminodiacetic acid)을 사용하였으며, IDA로 표기하였다. Iminodiacetic acid was used as an aminocarboxyl-based or aminophosphate-based compound, and is represented by IDA.
유기산, 무기산 또는 그들의 염에서 선택되는 어느 하나 또는 둘 이상의 화합물로 인산수소암모늄(ammonium hydrogen phosphate)을 사용하였으며, AHP로 표기하였다. Ammonium hydrogen phosphate was used as one or two or more compounds selected from organic acids, inorganic acids or salts thereof, and is designated as AHP.
불소화합물로 NH4HF2을 사용하였다. 언더컷억제제로 구아닌을 사용하였다. NH 4 HF 2 was used as the fluorine compound. Guanine was used as an undercut inhibitor.
C4 이상을 포함하는 알킬아민으로 부틸아민(butylamine), 펜틸아민(pentylamine), 헥실아민(hexylamine), 헵틸아민(heptylamine), 옥틸아민(octylamine) 및 에틸-1-헥실아민(2-Ethyl-1-hexylamine)을 사용하였다. Alkyl amines containing C 4 or more include butylamine, pentylamine, hexylamine, heptylamine, octylamine and ethyl-1-hexylamine (2-Ethyl- 1-hexylamine) was used.
부틸아민은 b-AM, 펜틸아민(pentylamine)은 pn-AM, 헥실아민(hexylamine)은 hx-AM, 헵틸아민(heptylamine)은 hp-AM, 옥틸아민(octylamine)은 o-AM, 2-에틸-1-헥실아민은 2-e-1-hx-A으로 표기하였다. Butylamine is b-AM, pentylamine is pn-AM, hexylamine is hex-AM, heptylamine is hp-AM, octylamine is o-AM, 2-ethyl -1-hexylamine is designated as 2-e-1-hx-A.
비교예에서는 알킬아민으로 프로필아민(propylamine), 에틸아민(ethylamine) 및 사이클로헥실아민(cyclohexylamine)을 사용하였으며, 프로필아민은 pr-AM, 에틸아민은 e-AM, 사이클로헥실아민은 cyhx-AM으로 표기하였다.In the comparative example, propylamine, ethylamine and cyclohexylamine were used as alkylamines, propylamine as pr-AM, ethylamine as e-AM, and cyclohexylamine as cyhx-AM. Notation is shown.
[시험예: 식각 성능 평가][Test Example: Etching Performance Evaluation]
유리기판 상에 두께 5500Å의 구리 막 및 몰리브덴 막을 각각 순차적으로 증착하여 시편을 제작하였다. 상기 시편에 대해 포토리소그래피 공정을 진행하여 패터닝한 레지스트막을 형성하고, 상기 실시예 1 내지 29, 및 비교예 1 내지 13의 식각액 조성물을 각각 이용하여 구리 및 몰리브덴 막에 대한 식각을 실시하였다. 이때, 상기 식각 공정은 스프레이가 가능한 장비(Mini-etcher ME-001)를 이용하여 32℃에서 120초 동안 실시하였다. A 5500 mm thick copper film and molybdenum film were sequentially deposited on a glass substrate to prepare a specimen. The specimen was subjected to a photolithography process to form a patterned resist film, and the copper and molybdenum films were etched using the etching solution compositions of Examples 1 to 29 and Comparative Examples 1 to 13, respectively. In this case, the etching process was carried out for 120 seconds at 32 ℃ using a sprayable equipment (Mini-etcher ME-001).
식각 완료 후 식각종말점을 측정하였다. 또한, 시디 로스(CD loss), 테이퍼 앵글 또는 구리 및 몰리브덴 막 계면의 과식각 발생 유무 등 식각된 구리 및 몰리브덴 막에 대한 식각 특성은 주사전자 현미경(Hitachi사, S-4800)을 이용하여 관찰하였다. 구리 및 몰리브덴 막 계면 과식각 유무는 시편을 틸트(tilt)하여 주사전자 현미경을 이용하여 확인하였다. 그 결과를 하기 표 2에 나타내었다.After completion of etching, the etching endpoint was measured. In addition, the etching characteristics of the etched copper and molybdenum films such as CD loss, taper angle or over-etching of the copper and molybdenum film interfaces were observed using a scanning electron microscope (Hitachi, S-4800). . The presence of copper and molybdenum film interface overetching was confirmed by scanning the microscope by tilting the specimen. The results are shown in Table 2 below.
식각종말점[초]Etch end point [second] CD loss[㎛]CD loss [㎛] 테이퍼 앵글 (°)Taper Angle (°) 구리/몰리브덴막계면의 과식각Overetching of copper / molybdenum film interface
실시예 1Example 1 8080 1.071.07 53.853.8 없음none
실시예 2Example 2 7575 1.161.16 46.146.1 없음none
실시예 3Example 3 7070 1.091.09 47.747.7 없음none
실시예 4Example 4 7070 1.081.08 47.547.5 없음none
실시예 5Example 5 7575 1.151.15 51.651.6 없음none
실시예 6Example 6 7575 1.111.11 45.945.9 없음none
실시예 7Example 7 8080 1.141.14 48.548.5 없음none
실시예 8Example 8 7070 1.121.12 50.250.2 없음none
실시예 9Example 9 7575 1.111.11 50.750.7 없음none
실시예 10Example 10 7070 1.121.12 54.454.4 없음none
실시예 11Example 11 7575 1.151.15 51.351.3 없음none
실시예 12Example 12 8080 1.161.16 53.353.3 없음none
실시예 13Example 13 7070 1.131.13 46.746.7 없음none
실시예 14Example 14 7575 1.061.06 55.055.0 없음none
실시예 15Example 15 7070 1.101.10 50.250.2 없음none
실시예 16Example 16 8080 1.191.19 49.949.9 없음none
실시예 17Example 17 7070 1.171.17 45.445.4 없음none
실시예 18Example 18 7070 1.111.11 49.749.7 없음none
실시예 19Example 19 7575 1.191.19 54.854.8 없음none
실시예 20Example 20 7070 1.081.08 46.146.1 없음none
실시예 21Example 21 8080 1.091.09 52.752.7 없음none
실시예 22Example 22 7575 1.111.11 49.549.5 없음none
실시예 23Example 23 7070 1.191.19 53.753.7 없음none
실시예 24Example 24 7575 1.081.08 53.553.5 없음none
실시예 25Example 25 7575 1.111.11 49.649.6 없음none
실시예 26Example 26 7575 1.141.14 50.850.8 없음none
실시예 27Example 27 7070 1.151.15 46.346.3 없음none
실시예 28Example 28 7575 1.151.15 46.046.0 없음none
실시예 29Example 29 7070 1.181.18 49.149.1 없음none
비교예 1Comparative Example 1 8080 1.151.15 69.069.0 있음has exist
비교예 2Comparative Example 2 7575 1.101.10 75.875.8 있음has exist
비교예 3Comparative Example 3 7070 1.111.11 74.074.0 있음has exist
비교예 4Comparative Example 4 7575 1.131.13 76.676.6 있음has exist
비교예 5Comparative Example 5 7070 1.091.09 62.462.4 있음has exist
비교예 6Comparative Example 6 7575 1.081.08 65.665.6 있음has exist
비교예 7Comparative Example 7 8080 1.101.10 76.676.6 있음has exist
비교예 8Comparative Example 8 7070 1.051.05 69.769.7 있음has exist
비교예 9Comparative Example 9 8585 1.201.20 77.377.3 있음has exist
비교예 10Comparative Example 10 7575 1.151.15 74.674.6 있음has exist
비교예 11Comparative Example 11 8080 1.181.18 78.678.6 있음has exist
비교예 12Comparative Example 12 7575 1.161.16 74.574.5 있음has exist
비교예 13Comparative Example 13 7575 1.031.03 68.368.3 있음has exist
상기 표 2는 식각 성능 평가를 나타낸 표이다. 상기 표 2에 나타난 바와 같이, 본 발명에 따른 실시예 1 내지 29의 식각 조성물은 C4 이상을 포함하는 알킬아민을 포함하여, 비교예 1 내지 13의 식각액 조성물과 비교하여, 에치 바이어스, 시디 로스(CD loss) 및 테이퍼 앵글에서 모두 우수한 결과를 나타내었다.Table 2 is a table showing the etching performance evaluation. As shown in Table 2, the etching composition of Examples 1 to 29 according to the present invention includes an alkylamine containing C 4 or more, compared to the etching solution composition of Comparative Examples 1 to 13, etch bias, CDi Ross Excellent results were obtained in both (CD loss) and taper angle.
특히, 실시예 4, 실시예 6, 실시예 11, 실시예 17 및 실시예 25의 경우, 불소화합물이 첨가되지 않은 실시예 5, 실시예 7, 실시예 12, 실시예 19 및 실시예 23과 각각 대비하였을 시, 과식각 제어 효과는 저하시키지 않으면서 몰리브덴막의 식각 속도를 향상시킬 수 있었으며, 이에 따라 테일렝스(tail length)가 감소하고 몰리브덴 잔사가 효과적으로 제거되었다.In particular, in Examples 4, 6, 11, 17 and 25, Example 5, Example 7, Example 12, Example 19, and Example 23, in which the fluorine compound was not added, In each case, the etching rate of the molybdenum film could be improved without deteriorating the over-etching control effect, thereby reducing tail length and effectively removing the molybdenum residue.
비교예 1 내지 7은 C3인 프로필아민을 포함하여, 구리막과 몰리브덴 막 계면으로 식각액 침투를 억제하는 역할을 하지 못하는 것을 알 수 있으며, 그 결과 과식각이 있는 것을 확인할 수 있다. 또한, 비교예 8은 C2인 에틸아민을 포함하여 과식각이 있는 것을 확인할 수 있다.Comparative Examples 1 to 7 include C 3 propylamine, it can be seen that it does not play a role of inhibiting the etching liquid penetration into the copper film and molybdenum film interface, and as a result it can be confirmed that there is over-etching. In addition, Comparative Example 8 can be confirmed that there is over-etching including ethylamine, which is C 2 .
비교예 9는 분자 내에 산소, 황 및 질소 중에서 선택되는 어느 하나 또는 둘 이상을 포함하는 환형 또는 방향족화합물인 5-아미노테크라졸(ATZ)을 포함하지 않아, 식각 속도 조절이 어렵고, 테이퍼 형태가 불량한 것을 확인할 수 있다. 비교예 10은 아미노카르복실계 또는 아미노인산계화합물인 이미노디아세트산(IDA)을 포함하지 않아 과산화수소 분해반응의 제어 능력이 떨어져 과식각이 발생한 것을 알 수 있다. 비교예 11은 유기산, 무기산 또는 그들의 염에서 선택되는 어느 하나 또는 둘 이상의 화합물인 인산수소암모늄(AHP)를 포함하지 않아 테이퍼 앵글 값이 높은 것을 알 수 있다. 비교예 12은 언더컷억제제인 구아닌을 포함하지 않아 몰리브덴 잔사가 발생하고, 테이퍼 앵글 값이 높은 것을 알 수 있다. 비교예 13는 고리형 아민 화합물인 사이클로헥실아민을 포함하여, 과식각 억제를 제어하지 못해 과식각이 발생한 것을 확인 할 수 있다.Comparative Example 9 does not include 5-aminotechazole (ATZ), which is a cyclic or aromatic compound including any one or two or more selected from oxygen, sulfur, and nitrogen in the molecule, so that the etching rate is difficult to control and the taper shape is poor. You can see that. Comparative Example 10 does not include the imino diacetic acid (IDA) of the amino carboxyl or amino phosphate compound, it can be seen that the over-etching occurred due to the poor control of the hydrogen peroxide decomposition reaction. Comparative Example 11 does not include ammonium hydrogen phosphate (AHP), which is one or two or more compounds selected from organic acids, inorganic acids, or salts thereof, and thus, the taper angle value is high. It can be seen that Comparative Example 12 does not contain guanine, which is an undercut inhibitor, so that molybdenum residue occurs and the taper angle value is high. Comparative Example 13 includes a cyclohexylamine which is a cyclic amine compound, and it can be confirmed that overetching has not occurred because the overetch inhibition is not controlled.
또한, 구리 및 몰리브덴 막 사이의 계면 과식각 발생 유무를 관찰하기 위하여, 실시예 1, 실시예 6 및 실시예 11과, 비교예 1 및 비교예 6의 식각액 조성물을 이용하여 식각된 구리 및 몰리브덴 막의 시편의 단편을 틸트(tilt)하여 주사전자현미경으로 관찰하였다. 그 결과를 도 1, 도 2, 도 3, 도 4 및 도 5에 나타내었다. In addition, in order to observe the presence of the interface over-etching between the copper and molybdenum film, the copper and molybdenum film etched using the etching liquid composition of Examples 1, 6 and 11 and Comparative Examples 1 and 6 A fragment of the specimen was tilted and observed by scanning electron microscopy. The results are shown in FIGS. 1, 2, 3, 4 and 5.
도 1은 실시예 1, 도 2는 실시예 6 및 도 3은 실시예 11에 따른 식각액 조성물을 이용하여 구리 및 몰리브덴 막을 식각한 후 시편의 단편을 틸트(tilt)하여 주사전자현미경으로 측면에서 관찰한 사진을 도시하였다.1 is an example 1, 2 is an example 6 and 3 is an etching liquid composition according to Example 11 after etching the copper and molybdenum film and then tilted the fragments of the specimen observed from the side with a scanning electron microscope One picture is shown.
도 4는 비교예 1, 도 5는 비교예 6에 따른 식각액 조성물을 이용하여 구리 및 몰리브덴 막을 식각한 후 시편의 단면을 틸트(tilt)하여 주사전자현미경으로 관찰한 사진을 도시하였다.4 is a comparative example 1, Figure 5 shows a photograph of the copper and molybdenum film using the etching solution composition according to Comparative Example 6 and then observed by a scanning electron microscope to tilt the cross section of the specimen.
도 1, 도 2, 도 3에 나타난 바와 같이, 본 발명인 실시예 1, 실시예 6, 실시예 11의 식각액 조성물을 이용하여 식각한 결과, 구리/몰리브덴 막 계면의 과식각이 관찰되지 않은 것을 확인할 수 있다.As shown in FIG. 1, FIG. 2, and FIG. 3, as a result of etching using the etchant compositions of Examples 1, 6 and 11 of the present invention, it was confirmed that the over-etching of the copper / molybdenum film interface was not observed. Can be.
그러나, 비교예 1 및 비교예 6의 식각액 조성물을 이용한 경우, 도 4 및 도 5에 나타난 바와 같이, 구리 및 몰리브덴 막 계면에서 과식각이 이루어져 계면 사이가 벌어지는 불량한 시각 프로파일을 확인 할 수 있다.However, in the case of using the etchant composition of Comparative Example 1 and Comparative Example 6, as shown in Figures 4 and 5, it is possible to confirm the poor visual profile of the gap between the interface by over-etching at the copper and molybdenum film interface.
또한, 에치(etch) 특성 확인을 위해 식각된 구리 및 몰리브덴 막의 시편의 단편을 주사전자현미경으로 관찰하였다. 그 결과를 도 6 및 도 7에 나타내었다. In addition, fragments of specimens of etched copper and molybdenum films were observed by scanning electron microscopy to confirm the etch characteristics. The results are shown in FIGS. 6 and 7.
도 6은 실시예 1에 따른 식각액 조성물을 이용하여 구리 및 몰리브덴 막을 식각한 후 시편의 단면을 주사전자현미경으로 관찰한 사진을 도시하였고, 도 7는 비교예 6에 따른 식각액 조성물을 이용하여 구리/몰리브덴 막을 식각한 후 시편의 단면을 주사전자현미경으로 관찰한 사진을 도시하였다.FIG. 6 illustrates a photograph of a specimen obtained by etching a copper and molybdenum film using an etchant composition according to Example 1, followed by scanning electron microscopy, and FIG. 7 using an etchant composition according to Comparative Example 6; After etching the molybdenum film, a cross-sectional view of the specimen was shown by scanning electron microscopy.
도 6에 나타난 바와 같이, 실시예 1의 식각액 조성물을 이용한 경우, 식각 특성이 우수한 것을 알 수 있다.As shown in Figure 6, when using the etching solution composition of Example 1, it can be seen that the etching characteristics are excellent.
도 7에 나타난 바와 같이, 비교예 6의 식각액 조성물을 이용한 경우, 구리 및 몰리브덴 막 계면의 과식각에 의해 역테이퍼 형태의 불량한 식각 특성을 보이는 것을 확인 할 수 있다.As shown in FIG. 7, when the etching solution composition of Comparative Example 6 is used, it may be confirmed that the etching property of the reverse taper is poor due to the overetching of the copper and molybdenum film interfaces.
상기와 같이, 본 발명에 따른 식각액 조성물은 구리 및 몰리브덴 막의 식각 시, 구리 및 몰리브덴 막 계면의 과식각을 제어하여 안정적인 식각 공정을 가능함을 알 수 있다. 또한, 그 결과로 테이퍼 앵글, 시디 로스 및 시각 직진성 등의 식각 특성을 개선시킴을 확인할 수 있다. As described above, it can be seen that the etching liquid composition according to the present invention enables a stable etching process by controlling overetching of the copper and molybdenum film interfaces when etching the copper and molybdenum films. In addition, it can be seen that the results improve the etching characteristics such as taper angle, CD loss and visual straightness.
이상에서 본 발명의 바람직한 실시예를 설명하였으나, 본 발명은 다양한 변화와 균등물을 사용할 수 있으며, 상기 실시예를 적절히 변형하여 동일하게 응용할 수 있음이 명확하다. 따라서, 상기 기재 내용은 하기의 특허청구범위의 한계에 의해 정해지는 본 발명의 범위를 한정하는 것은 아니다.Although the preferred embodiment of the present invention has been described above, it is clear that the present invention can use various changes and equivalents, and can be applied in the same manner by appropriately modifying the above embodiment. Accordingly, the above description does not limit the scope of the invention as defined by the following claims.

Claims (13)

  1. 과산화수소; 분자 내에 산소, 황 및 질소 중에서 선택되는 어느 하나 또는 둘 이상을 포함하는 환형 또는 방향족화합물; 아미노카르복실계 또는 아미노인산계화합물; 유기산, 무기산 또는 그들의 염에서 선택되는 어느 하나 또는 둘 이상의 화합물; 언더컷억제제; 및 C4 이상을 포함하는 알킬아민을 포함하는 식각액 조성물.Hydrogen peroxide; Cyclic or aromatic compounds containing any one or two or more selected from oxygen, sulfur and nitrogen in the molecule; Aminocarboxylic or amino phosphate compounds; Any one or two or more compounds selected from organic acids, inorganic acids or salts thereof; Undercut inhibitors; And alkylamine comprising C 4 or more.
  2. 제 1항에 있어서,The method of claim 1,
    상기 식각액 조성물은 과산화수소 100 중량부를 기준으로, 환형 또는 방향족 화합물 0.1 내지 50 중량부; 아미노카르복실계 또는 아미노인산계화합물 0.1 내지 50 중량부; 유기산, 무기산 또는 그들의 염에서 선택되는 어느 하나 또는 둘 이상의 화합물 0.1 내지 50 중량부; 언터컷억제제 0.01 내지 20 중량부; 및 알킬아민 0.1 내지 50 중량부를 포함하는 식각액 조성물.The etchant composition is based on 100 parts by weight of hydrogen peroxide, 0.1 to 50 parts by weight of a cyclic or aromatic compound; 0.1 to 50 parts by weight of an aminocarboxyl or aminophosphate compound; 0.1 to 50 parts by weight of any one or two or more compounds selected from organic acids, inorganic acids or salts thereof; 0.01 to 20 parts by weight of an undercut inhibitor; And 0.1 to 50 parts by weight of alkylamine.
  3. 제 1항에 있어서,The method of claim 1,
    상기 식각액 조성물은 불소화합물을 더 포함하는 식각액 조성물.The etchant composition further comprises a fluorine compound.
  4. 제 3항에 있어서,The method of claim 3, wherein
    상기 불소화합물은 과산화수소 100 중량부를 기준으로, 0.01 내지 20 중량부로 첨가되는 식각액 조성물.The fluorine compound is an etching solution composition is added to 0.01 to 20 parts by weight based on 100 parts by weight of hydrogen peroxide.
  5. 제 1항에 있어서,The method of claim 1,
    상기 C4 이상을 포함하는 알킬아민은 C4 내지 C16을 포함하는 직쇄형 또는 분지쇄형의 알킬아민 화합물인 식각액 조성물.The alkylamine comprising a C 4 or more is an etchant composition of a straight or branched chain alkylamine compound containing C 4 to C 16 .
  6. 제 5항에 있어서,The method of claim 5,
    상기 C4 이상을 포함하는 알킬아민은 부틸아민, 펜틸아민, 헥실아민, 헵틸아민, 옥틸아민 및 2-에틸-1-헥실아민에서 선택되는 어느 하나 또는 둘 이상의 혼합물인 식각액 조성물.The alkylamine comprising at least C 4 is an etch liquid composition of any one or two or more selected from butylamine, pentylamine, hexylamine, heptylamine, octylamine and 2-ethyl-1-hexylamine.
  7. 제 1항에 있어서,The method of claim 1,
    상기 환형 또는 방향족화합물은 옥사졸, 이미다졸, 피라졸, 트리아졸, 테트라졸, 5-아미노테트라졸, 메틸테트라졸, 피페라진, 메틸피페라진, 히드록실에틸피페라진, 벤즈이미다졸, 벤즈피라졸, 톨루트리아졸, 히드로톨루트리아졸 및 히드록시톨루트리아졸에서 선택되는 어느 하나 또는 둘 이상의 혼합물인 식각액 조성물.The cyclic or aromatic compound may be oxazole, imidazole, pyrazole, triazole, tetrazole, 5-aminotetrazole, methyltetrazole, piperazine, methylpiperazine, hydroxylethylpiperazine, benzimidazole, benzpyrazine Etch liquid composition is any one or a mixture of two or more selected from sol, tolutriazole, hydrotolutriazole and hydroxytolutriazole.
  8. 제 1항에 있어서, The method of claim 1,
    상기 아미노카르복실계 또는 아미노인산계화합물은 분자내 아미노기와 함께, 카르복실산기 또는 포스폰산기를 포함하는 것인 식각액 조성물.The aminocarboxylic acid or amino phosphate compound is an etching solution composition comprising a carboxylic acid group or a phosphonic acid group, together with the amino group in the molecule.
  9. 제 1항에 있어서, The method of claim 1,
    상기 아미노카르복실계 또는 아미노인산계화합물은 이미노디아세트산, 니트릴로트리아세트산, 에틸렌디아민테트라아세트산, 디에틸렌트리니트릴펜타아세트산, 아미노트리스(메틸렌포스폰산), (1-히드록시에탄-1,1-디일)비스(포스폰산), 에틸렌디아민 테트라(메틸렌포스폰산), 디에틸렌트리아민 펜타(메틸렌포스폰산), 알라닌, 글루탐산, 아미노부티르산 및 글리신에서 선택되는 어느 하나 또는 둘 이상의 혼합물인 식각액 조성물. The aminocarboxylic or amino phosphate compound is imino diacetic acid, nitrilotriacetic acid, ethylenediamine tetraacetic acid, diethylenetrinitrile pentaacetic acid, aminotris (methylenephosphonic acid), (1-hydroxyethane-1,1- An etchant composition which is any one or a mixture of diyl) bis (phosphonic acid), ethylenediamine tetra (methylenephosphonic acid), diethylenetriamine penta (methylenephosphonic acid), alanine, glutamic acid, aminobutyric acid and glycine.
  10. 제 1항에 있어서, The method of claim 1,
    상기 유기산은 아세트산, 포름산, 부탄산, 시트르산, 글리콜산, 옥살산, 말론산, 펜탄산, 프로피온산, 타르타르산, 글루콘산, 글리코산 및 숙신산에서 선택되는 어느 하나 또는 둘 이상의 혼합물이고,The organic acid is any one or a mixture of two or more selected from acetic acid, formic acid, butanoic acid, citric acid, glycolic acid, oxalic acid, malonic acid, pentanic acid, propionic acid, tartaric acid, gluconic acid, glycoic acid and succinic acid,
    상기 무기산은 황산, 질산 및 인산에서 선택되는 어느 하나 또는 둘의 혼합물이고,The inorganic acid is any one or a mixture of two selected from sulfuric acid, nitric acid and phosphoric acid,
    상기 무기산염 및 유기산염은 인산수소칼륨, 인산수소나트륨, 인산수소암모늄, 인산나트륨, 과인산나트륨, 인산칼륨, 과인산칼륨, 인산암모늄 및 과인산암모늄에서 선택되는 어느 하나 또는 둘 이상의 혼합물인 식각액 조성물.The inorganic acid salt and the organic acid salt is an etching liquid composition of any one or two or more selected from potassium hydrogen phosphate, sodium hydrogen phosphate, ammonium hydrogen phosphate, sodium phosphate, sodium perphosphate, potassium phosphate, potassium perphosphate, ammonium phosphate and ammonium perphosphate.
  11. 제 3항에 있어서,The method of claim 3, wherein
    상기 불소화합물은 HF, NaF, KF, AlF3 , HBF, NH4HF2, NaHF2, KHF2 및 NH4BF4에서 선택되는 어느 하나 또는 둘 이상의 혼합물인 식각액 조성물.The fluorine compound is HF, NaF, KF, AlF 3 , HBF, NH 4 HF 2 , NaHF 2 , KHF 2 And NH 4 BF 4 , wherein the etchant composition is one or a mixture of two or more thereof.
  12. 제 1항에 있어서, The method of claim 1,
    상기 언더컷 억제제는 아데닌, 구아닌, 이소구아닌, 하이포크산틴, 크산틴, 테오브로민, 카페인 및 유린산에서 선택되는 하나 또는 둘 이상의 혼합물인 식각액 조성물.The undercut inhibitor is one or two or more mixtures selected from adenine, guanine, isoguanine, hypoxanthine, xanthine, theobromine, caffeine and urinic acid.
  13. 제 1항에 있어서,The method of claim 1,
    상기 식각액 조성물은 과수안정제, 식각안정제 및 글라스 식각억제제에서 선택되는 어느 하나 또는 둘 이상의 첨가제를 더 포함하는 식각액 조성물. The etchant composition further comprises any one or two or more additives selected from a fruit water stabilizer, an etching stabilizer and a glass etching inhibitor.
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