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WO2017086758A1 - Composition pour la gravure de cuivre, et composition à base de peroxyde d'hydrogène pour la gravure de métal - Google Patents

Composition pour la gravure de cuivre, et composition à base de peroxyde d'hydrogène pour la gravure de métal Download PDF

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Publication number
WO2017086758A1
WO2017086758A1 PCT/KR2016/013412 KR2016013412W WO2017086758A1 WO 2017086758 A1 WO2017086758 A1 WO 2017086758A1 KR 2016013412 W KR2016013412 W KR 2016013412W WO 2017086758 A1 WO2017086758 A1 WO 2017086758A1
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WIPO (PCT)
Prior art keywords
acid
hydrogen peroxide
group
copper
etching composition
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Ceased
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PCT/KR2016/013412
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English (en)
Korean (ko)
Inventor
김윤철
박종희
권윤경
장욱
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OCI Holdings Co Ltd
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OCI Co Ltd
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Publication date
Priority claimed from KR1020150162226A external-priority patent/KR101669772B1/ko
Priority claimed from KR1020150162229A external-priority patent/KR101695571B1/ko
Application filed by OCI Co Ltd filed Critical OCI Co Ltd
Priority to CN201680068003.6A priority Critical patent/CN108291314B/zh
Priority to JP2018526545A priority patent/JP6670934B2/ja
Publication of WO2017086758A1 publication Critical patent/WO2017086758A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof

Definitions

  • the present invention relates to a composition for etching copper or a composition for hydrogen peroxide-based metal etching, and more particularly, a composition for etching copper, which can suppress the generation of copper precipitates from the composition for etching by increasing the stability of the chelate bond formed between copper and the organic material.
  • the present invention relates to a hydrogen peroxide-based metal etching composition capable of preventing decomposition of hydrogen peroxide in a composition and denaturation of other components.
  • BACKGROUND ART Semiconductor devices, display devices, printed circuit boards, IC cards and the like generally form metal thin film elements, electrode wiring elements, and the like by patterning a metal thin film or the like on a substrate.
  • a wet etching patterned by etching with chemicals using a photoresist pattern formed on the metal thin film surface by photolithography as a mask As a processing technique for patterning such a metal thin film into a fine structure such as wiring, a wet etching patterned by etching with chemicals using a photoresist pattern formed on the metal thin film surface by photolithography as a mask. And dry etching such as ion etching or plasma etching.
  • the wet etching method is economically advantageous because it does not require an expensive device, unlike the dry etching method, and uses a relatively inexpensive chemical.
  • metal thin film elements As a material used for metal thin film elements, electrode wirings, and other elements used in semiconductors and liquid crystal displays, and the like, copper, titanium, molybdenum, or alloys thereof having low electrical resistance and easy processability into thin film patterns Metals are preferred.
  • metal etchant (or a composition for metal etching) is essential.
  • Most metal etchant has a hydrogen peroxide-based etchant having excellent cost and performance.
  • Hydrogen peroxide-based etchant is prepared by mixing chelating agents and other additives with hydrogen peroxide. When excess copper is dissolved into the etchant as the copper is etched, unstable hydrogen peroxide is decomposed and the performance of the etchant is often found. It became.
  • Such a copper precipitate may cause problems such as impairing the performance of the hydrogen peroxide-based etchant in the chamber where copper is etched or being precipitated in a pipe or the like and inhibiting the flow of liquid.
  • Hydrogen peroxide-based etchant is another problem, and the quality characteristics of the etching result are changed by chemical action between various components contained in the etchant, and particularly over time (EPD change, residue occurrence, stability of etchant, etc.). Will make a big difference.
  • An object of the present invention is to provide a composition for etching copper, which can suppress the generation of copper precipitates from the composition for etching by increasing the stability of the chelate bond formed between the copper and the organic material.
  • an object of the present invention is to provide a copper etching composition which can prevent the dissolved copper from being precipitated as a precipitate as hydrogen peroxide is decomposed when an excessive amount of copper is dissolved into the composition for etching.
  • an object of the present invention is to provide a composition for etching copper, which can reduce the decomposition potential of hydrogen peroxide by copper by increasing the dissolving power of the composition for etching.
  • Another object of the present invention is to provide a hydrogen peroxide-based metal etching composition having excellent stability over time.
  • another object of the present invention is to provide a hydrogen peroxide-based metal etching composition which can prevent the decomposition of hydrogen peroxide in the hydrogen peroxide-based metal etching composition to prevent a sharp drop in the concentration of hydrogen peroxide.
  • the present invention improves the stability of the hydrogen peroxide-based metal etching composition by reducing the chemical modification of the other components in the hydrogen peroxide-based metal etching composition, and to provide a composition for hydrogen peroxide-based metal etching that can maintain the etching ability for a long time The purpose.
  • hydrogen peroxide may include at least one chelating agent selected from an acetic acid chelating agent, a sulfonic acid chelating agent and a phosphonic acid chelating agent; Chelate stabilizers represented by the following formula (1); And water; may include a copper etching composition comprising a.
  • R 1 to R 3 are C 1 -C 3 alkyl.
  • At least one main chelating agent selected from hydrogen peroxide, acetic acid-based chelating agent and amino acid-based chelating agent, sulfuric acid-based first sub chelating agent represented by the following formula 11 or formula 12 or salts thereof,
  • a hydrogen peroxide-based metal etching composition including a phosphate-based second subchelating agent represented by Formula 13 or Formula 14 or a salt thereof, an etching inhibitor, and water may be provided.
  • R 1 to R 3 are each independently hydrogen, a hydroxyl group, a halogen group, an amino group, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 1 -C 10 haloalkyl group, a C 1 -C 10 aminoalkyl group , Phenyl group and halogen-substituted phenyl group,
  • R 4 to R 12 are each independently hydrogen, a hydroxyl group, a halogen group, an amino group, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 1 -C 10 haloalkyl group, a C 1 -C 10 aminoalkyl group , Phenyl group and halogen-substituted phenyl group.
  • the said nitrogen atom is a 1, 2 or tetrasubstituted nitrogen atom.
  • the nitrogen atom is preferably a 1, 2 or tetrasubstituted nitrogen atom.
  • At least one carbon atom may be substituted with a functional group selected from carboxy group, amino group, amide group, carbamoyl group, nitro group and acetyl group. have.
  • Copper etching composition according to an embodiment of the present invention can increase the stability of the chelating bond formed between the copper and the organic material by including a chelating stabilizer with a chelating agent to suppress the generation of copper precipitates from the etching composition.
  • the copper etching composition according to the present invention can further increase the maximum concentration of soluble copper ions in the etching composition by the additional chelate effect of the chelate stabilizer, thereby preventing decomposition of hydrogen peroxide by excess copper. Can be.
  • Hydrogen peroxide-based metal etching composition according to another embodiment of the present invention is excellent in stability during long-term storage or use is less likely to decompose hydrogen peroxide in the composition.
  • the hydrogen peroxide-based metal etching composition according to the present invention can inhibit the chemical modification of the composition by preventing side reactions between the hydrogen peroxide and other components in the composition, thereby maintaining the etching ability of the hydrogen peroxide-based metal etching composition for a long time have.
  • Copper etching composition according to an aspect of the present invention as a hydrogen peroxide-based etchant for wet etching of copper may include hydrogen peroxide, chelating agent, chelate stabilizer and water.
  • the hydrogen peroxide is a hydrogen peroxide-based metal etching composition for the hydrogen peroxide-based metal etching as a proton donor (hydrogen donor) at the same time as a main oxidant to have an etching ability to the metal, such as copper, titanium or molybdenum Contribute to the stability of the composition.
  • hydrogen peroxide can etch metals such as copper or molybdenum through mechanisms such as Scheme 1 and Scheme 2 below.
  • hydrogen peroxide may be included in an amount of 5 to 40 wt% based on the total weight of the metal etching composition.
  • the content of hydrogen peroxide contained in the metal etching composition is less than 5% by weight, there is a concern that the etching ability for metals such as copper or molybdenum may be insufficient, so that the etching may not be performed well or the etching rate may be too slow to be used commercially.
  • the chelating agent may be at least one chelating agent selected from an acetic acid chelating agent, a sulfonic acid chelating agent and a phosphonic acid chelating agent.
  • the acetic acid chelating agent is nitrilotriacetic acid, imino diacetic acid, methylimino diacetic acid, hydroxyethylimino diacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetetraacetic acid At least one selected from methylethylenediaminetetraacetic acid and triethylenetetraaminehexaacetic acid.
  • the sulfonic acid chelating agent may be at least one selected from sulfonic acid, methanesulfonic acid, methanedisulfonic acid, ethanesulfonic acid, ethanedisulfonic acid, propanesulfonic acid, benzenesulfonic acid, chlorobenzenesulfonic acid and ethylbenzenesulfonic acid. have.
  • the phosphonic acid-based chelating agent may be at least one selected from ethylenediaminetetramethylenephosphonic acid, diethylene triaminepentamethylenephosphonic acid, hydroxyethylidenediphosphonic acid and aminotrimethylene phosphonic acid.
  • imino diacetic acid which may be used as a chelating agent of the copper etching composition according to an embodiment of the present invention, has a form in which two carboxyl groups are bonded to nitrogen, which is a central atom, as shown in Formula 2 below.
  • the metal forms chelate bonds with nitrogen, the central atom, and oxygen of the two carboxyl groups, as shown in Formula 3 below. Can be.
  • the metal (M) forms three bonds with one nitrogen atom and two oxygen atoms in one molecule of iminodiacetic acid, and the metal (M) is represented by By further forming one bond with nodiacetic acid, stable chelate bonds can be maintained.
  • the chelate bond of the structure represented by the formula (3) is unstable chelated state of the metal (M), when left in this state, can be precipitated as a precipitate in the form of copper-iminodiacetic acid.
  • R 1 to R 3 may be C 1 -C 3 alkyl, that is, an alkyl chain having 1 to 3 carbon atoms.
  • the chelate stabilizer represented by Formula 1 is similar to iminodiacetic acid, and after removal of acidic protons of two carboxyl groups bound to a nitrogen atom, which is a central atom, the metal (M; for example, copper) is represented by Formula 5 below. Chelate bonds can be formed.
  • the chelating stabilizer provides additional chelating bonds to the copper formed with unstable chelating bonds, as shown in Formula 6, to prevent the occurrence of copper precipitates, as well as to consume the chelating agent to form additional chelate bonds with copper. The amount can be reduced.
  • the copper etching composition may include 5 to 40 parts by weight of hydrogen peroxide, 1 to 2 parts by weight of chelating agent, 0.1 to 0.4 parts by weight of chelating stabilizer, and a balance of water.
  • the weight ratio of the chelating agent to the chelating stabilizer in the copper etching composition is preferably 1: 0.1 to 1: 0.4.
  • the ratio of the chelating agent and the chelating stabilizer is 1: 0.1 or less, that is, when the content of the chelating stabilizer is excessively small relative to the content of the chelating agent in the copper etching composition, the chelating agent and the unstable chelate, as shown in the formula (6) Stabilizing effect can be negligible by providing additional chelate bonds to the copper that formed the bonds.
  • the ratio of the chelating agent and the chelating stabilizer is 1: 0.4 or more, that is, the content of the chelating stabilizer to the content of the chelating agent in the copper etching composition is higher than or equal to a predetermined standard, the entire copper etching composition (solvent in which the solute is dissolved) Since the amount of chelating agent and chelating stabilizer that can be dissolved into is limited, there is a possibility that the chelating agent and / or chelating stabilizer is not completely dissolved but is present in the precipitate state.
  • the maximum concentration of soluble copper ions in the copper etching composition according to an embodiment of the present invention is 6000 ppm or more, it is possible to implement a stable etching characteristics without decomposition of hydrogen peroxide and / or copper precipitates.
  • the copper etching composition according to an embodiment of the present invention can solve the problem of precipitation of copper due to unstable chelating bonds by chelating bonds of copper ions by chelating agents and additional chelating bonds by chelating stabilizers, In addition, by additionally supplying a chelating stabilizer, the possibility that two molecules of the chelating agent is consumed for chelating bond of one copper ion with the chelating ion is significantly reduced, even though the same amount of chelating agent is included in one embodiment of the present invention.
  • the copper etching composition according to the present invention has a maximum concentration of soluble copper ions, thereby increasing the life of the copper etching composition, and preventing decomposition of hydrogen peroxide by excessive copper.
  • Hydrogen peroxide-based metal etching composition according to another aspect of the present invention as a hydrogen peroxide-based etchant for the wet etching of copper may include hydrogen peroxide, main chelating agent, sub chelating agent, etching inhibitor and water.
  • the metal etching composition according to an embodiment of the present invention further includes a main chelating agent together with hydrogen peroxide.
  • the main chelating agent assists in etching the metal and at the same time forms a chelating bond with the oxidized form of the metal (ie, metal ions), thereby increasing the stability of the metal ions.
  • 0.1 to 5% by weight may be included.
  • the content of the main chelating agent contained in the metal etching composition is less than 0.1% by weight, chelate to metal ions such as copper or molybdenum dissolved in the metal etching composition by the main oxidant is insufficient, resulting in precipitation or excessive dissolution of metal ions. There is a possibility that the etching ability of the metal etching composition is disrupted by the decomposition of hydrogen peroxide by the used metal ions.
  • the etching control is not easy due to the main chelating agent present in excess, or the main chelating agent is precipitated because it exceeds the solubility of the general main chelating agent. Can cause problems.
  • acetic acid chelating agents and / or amino acid chelating agents may be used as the main chelating agent.
  • the acetic acid chelating agent may be at least one selected from imino diacetic acid, methylimino diacetic acid, iminomalonic acid and hydroxyethylimino diacetic acid.
  • the amino acid chelating agent may be at least one selected from alanine, glutamic acid, aminobutyric acid and glycine.
  • imino diacetic acid which can be used as the main chelating agent, has a form in which two carboxyl groups are bonded to nitrogen, which is a central atom, as shown in the following Formula 15.
  • the metal for example, divalent copper ions
  • the metal chelates with nitrogen as the central atom and oxygen of the two carboxyl groups as shown in the following formula (16). Can be formed.
  • the metal (M) forms three bonds with one nitrogen atom and two oxygen atoms in one molecule of iminodiacetic acid, and the metal (M) is an iminodi of another molecule as shown in Formula 17 below.
  • the metal (M) is an iminodi of another molecule as shown in Formula 17 below.
  • the chelate bond of the structure represented by the formula (16) is a state in which the metal (M) is unstable chelated, and when left in this state for a long time, it may precipitate as a precipitate in the form of metal-iminodiacetic acid.
  • the present invention even if the amount of metal ions dissolved into the metal etching composition is increased, it further comprises a subchelating agent in the metal etching composition so that it is possible to form a stable chelate bond represented by the formula (17). Characterized in that.
  • the subchelating agent included in the metal etching composition not only assists the chelating bond of the main chelating agent to the metal ions, but also has a certain level of metal etching ability, and maintains pickling of the metal etching composition to maintain the metal etching composition. It can increase the stability and pH retention.
  • the metal etching composition according to an embodiment of the present invention is represented by the sulfuric acid-based first sub chelating agent (or a salt thereof) represented by the following formula (11) or (12) and represented by the following formula (13) or formula (14) It may further comprise a phosphoric acid-based second sub chelating agent (or a salt thereof).
  • R 1 to R 3 independently of each other, a hydrogen, a hydroxyl group, a halogen group, an amino group, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 1 -C 10 haloalkyl group , C 1 -C 10 aminoalkyl group, a phenyl group and a halogen-substituted phenyl group
  • R 4 to R 12 in the formula (13) and the formula (14) can be independently of each other hydrogen, hydroxy, halogen, amino, It may be selected from C 1 -C 10 alkyl group, C 1 -C 10 alkoxy group, C 1 -C 10 haloalkyl group, C 1 -C 10 aminoalkyl group, phenyl group and halogen-substituted phenyl group.
  • At least one carbon atom is selected from a carboxy group, an amino group, an amide group, a carbamoyl group, a nitro group, and an acetyl group. Can be substituted with a functional group.
  • the sulfuric acid first subchelating agent (or a salt thereof) represented by Formula 11 or Formula 12 and the phosphoric acid second subchelating agent (or a salt thereof) represented by Formula 13 or Formula 14 below are represented by an oxygen or nitrogen atom.
  • the nitrogen atom is preferably a 1, 2 or tetrasubstituted nitrogen atom.
  • the metal etching composition according to an embodiment of the present invention includes hydrogen peroxide having a strong oxidizing power, and hydrogen peroxide may cause an oxidation reaction with other compounds in the metal etching composition.
  • R 3 N + H 2 O 2 ⁇ R 3 N + -O - + H 2 O
  • aminotris methylenephosphonic acid
  • metal etching composition since it has three phosphonic acid substituents, it has a pKa value of six steps in the range of 0.3-12.2.
  • the aminotris methylenephosphonic acid
  • aminotris methylenephosphonic acid
  • aminotris has a plurality of phosphonic acid substituents that can assist chelation of metal ions, and at the same time, a composition for etching metals by stepwise proton supply characteristics by a plurality of phosphonic acid substituents It is mainly used as a chelating agent.
  • aminotris (methylenephosphonic acid) is a tertiary amine compound, and may react with hydrogen peroxide to form N-oxide as shown in Scheme 4 below.
  • the N + -O - bond of the N-oxide produced by the above Scheme 4 is a coordination bond and a bond by donation of the outermost electron of the nitrogen atom.
  • the nitrogen atom and the oxygen atom are substantially in a state where the charge is separated.
  • N + -O - coordination bond has a polarity by the charge separation of the nitrogen and oxygen atoms as described above, the polarity of the N + -O - coordination bond is characterized in the characteristics of the phosphonic acid substituent bonded to the nitrogen atom, in particular pKa Will be affected.
  • the reaction scheme Side reactions of hydrogen peroxide with chelating agents, such as 4, act as a cause of changing the pH of the metal etch composition as well as the pKa of the chelating agent (main chelating agent and / or sub chelating agent).
  • the nitrogen atom is preferably not a trisubstituted nitrogen atom.
  • the first subchelating agent and the second subchelating agent included in the metal etching composition according to an embodiment of the present invention is preferably a compound other than a compound containing a tertiary amine or a tertiary amino group, and the main chelate
  • the agent is also preferably a compound other than a compound containing a tertiary amine or tertiary amino group.
  • At least one compound selected from iminodiacetic acid, methyliminodiacetic acid, iminomalonic acid, hydroxyethyliminodiacetic acid, alanine, glutamic acid, aminobutyric acid and glycine may be used.
  • the first subchelating agent sulfonic acid, methanesulfonic acid, methanedisulfonic acid, ethanesulfonic acid, ethanedisulfonic acid, propanesulfonic acid, benzenesulfonic acid, chlorobenzenesulfonic acid, ethylbenzenesulfonic acid, potassium bisulfate, potassium At least one compound selected from sulfate, sodium bisulfate, sodium sulfate, ammonium sulfate, ammonium persulfate, dimethyl sulfoxide and diethyl sulfoxide may be used, and the second subchelating agent may be aminoethylphosphonic acid, carboxyethyl At least one selected from phosphonic acid, dimethylphosphate, dimethylphosphonate, hydroxyethylidenediphosphonic acid, methylenediphosphonic acid, hydroxyphosphonocarboxylic acid, methylenediphosphonocarboxylic acid,
  • chelating agents which are not suitable for the metal etching composition according to an embodiment of the present invention include aminotris (methylenephosphonic acid), N, N-bis (phosphonomethyl) glycine, Diethylenetriaminepenta (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), N- (phosphonomethyl) iminodiacetic acid, tetramethylenediaminetetra (methylene Phosphonic acid).
  • the first subchelating agent and the second subchelating agent in the metal etching composition is preferably used in combination.
  • the content of the first sub chelating agent in the metal etching composition is preferably 0.5 to 2.0% by weight
  • the content of the second sub chelating agent is preferably 0.1 to 1.6% by weight.
  • the weight ratio of the first subchelating agent and the second subchelating agent in the metal etching composition is preferably in the range of 6: 4 to 9: 1.
  • the first subchelating agent which can be used according to an embodiment of the present invention is a sulfuric acid-based chelating agent has excellent stability over time, while the second subchelating agent is a phosphate-based chelating agent of the metal etching ability and the composition for etching metal Pickling retention is excellent.
  • the weight ratio of the first subchelating agent and the second subchelating agent in the metal etching composition is less than 6: 4 (for example, 0.5: 9.5)
  • the stability of the metal etching composition with time decreases, thereby changing the time and the amount of metal.
  • the EPD may be slowed, or the etchable component of the metal etching composition may be more likely to be decomposed.
  • the EPD may be slowed due to insufficient etching ability of the metal, Poor pickling retention may reduce the pH stability of the metal etching composition.
  • the main chelating agent may not be able to sufficiently perform the chelating assistant role, and as a proton donor. May have insufficient ability to act to stabilize the pH of the metal etching composition.
  • the content of the first sub chelating agent and the second sub chelating agent contained in the metal etching composition exceeds 2% by weight and 1.6% by weight, respectively, it is not easy to control the etching by the excessively present subchelating agent Otherwise, there may occur a problem that precipitates exceeding the solubility of the sub chelating agent in the metal etching composition.
  • composition for etching metal according to an embodiment of the present invention may further include an etching inhibitor to obtain an etching result of excellent quality by adjusting the etching rate of the metal.
  • the etching inhibitor may be included in an amount of 0.5 to 1.5 wt% based on the total weight of the metal etching composition.
  • the content of the etching inhibitor contained in the metal etching composition is less than 0.5% by weight, there is a possibility that the etching rate of the metal may be excessively high and the quality of the etching result may decrease, whereas the content of the etching inhibitor contained in the metal etching composition is 1.5. If the weight percentage is exceeded, there is a possibility that the etching rate is lowered and the productivity is lowered.
  • the etching inhibitor included in the metal etching composition according to an embodiment of the present invention is preferably a compound other than a compound containing a tertiary amine or a tertiary amino group.
  • etching inhibitors include furan, thiophene, pyrrole, oxazole, imidazole, pyrazole, triazole, tetrazole, aminotetrazole, methyltetrazole, piperazine, methylpiperazine, hydroxyethylpiperazine, At least one compound selected from pyrrolidine, aloxane, benzofuran, benzothiophene, indole, benzimidazole, benzpyrazole, tolutriazole, hydrotolutriazole and hydroxytolutriazole is used.
  • the pyridine-based compound capable of reacting with hydrogen peroxide to form N-oxide is not suitable as an etching inhibitor used in the metal etching composition according to the embodiment of the present invention.
  • the metal etching composition according to an embodiment of the present invention may further include additional components such as a corrosion inhibitor, a surfactant, a pH adjusting agent, an undercut inhibitor or a residue inhibitor.
  • Table 1 shows the compositions of the copper etching compositions according to Examples and Comparative Examples.
  • the copper etching composition according to the Examples and Comparative Examples were put into the spray equipment of wet etching method (manufactured by KCTECH, model name: ETCHER (TFT)) Etching was performed on a copper substrate with a thickness of 2000 kPa when the temperature was maintained at 33 ⁇ 0.5 ° C. by heating.
  • wet etching method manufactured by KCTECH, model name: ETCHER (TFT)
  • the characteristic evaluation item for evaluating the stability of the copper etching composition is whether or not the etchant generated precipitates at a copper ion concentration of 6000 ppm and the concentration of copper ions that can be dissolved in maximum.
  • Examples 1 to 4 are copper etching compositions comprising an acetic acid-based chelating agent
  • Examples 5 and 6 are copper etching compositions comprising a sulfonic acid-based chelating agent
  • Examples 7 and 8 are phosphone
  • Examples 1 to 8 included the chelating stabilizer represented by the formula (7) or formula (8) in an amount of 0.1 to 0.4% by weight relative to the weight of the total copper etching composition.
  • Comparative Example 1 and Comparative Example 2 is a copper etching composition containing only a chelating agent without a chelating stabilizer, although the maximum soluble copper ion concentration increases as the content of the chelating agent increases, copper-iminodiacetic acid It was confirmed that a precipitate of the form occurred.
  • Comparative Examples 3 to 5 includes an iminodiacetic acid as an acetic acid-based chelating agent, and further includes a component (for example, an auxiliary chelating agent) that is usually used as an additive of a copper etching composition.
  • a component for example, an auxiliary chelating agent
  • the composition further comprises N-methyliminodiacetic acid, N, N-bis (carboxymethyl) ethanolamine and triethylenetetraaminehexaacetic acid as auxiliary chelating agents
  • the maximum soluble copper ion concentration of the copper etching composition is It was confirmed that the commercialization level was reached at 7500 to 9000 ppm.
  • This phenomenon is a compound having a different structure from the chelate stabilizer represented by the formula 1, N-methylimino diacetic acid, N, N-bis (carboxymethyl) ethanolamine and triethylene tetraamine hexaacetic acid,
  • the stabilizer was not able to provide an effect of compensating for the unstable chelating bond between the copper ions and the chelating agent, and it was confirmed that the copper-chelating agent forming the unstable chelating bond was precipitated in the form of a precipitate.
  • the composition for etching copper according to Comparative Example 6 includes an imino diacetic acid as the acetic acid-based chelating agent, as in the embodiment of the present invention contained a chelating stabilizer represented by the formula (7).
  • the content of the chelate stabilizer is 0.05% by weight relative to the weight of the total copper etching composition, which is lower than the content of the chelate stabilizer included in the examples.
  • Comparative Examples 7 and 9 each containing a sulfonic acid chelating agent or a phosphonic acid chelating agent alone, Comparative Example 8 and a phosphonic acid chelating agent and an auxiliary chelating agent are used in combination.
  • Comparative Example 10 in which a mixture is used, as the etching proceeds, it was confirmed that the copper precipitates were generated even though the maximum dissolvable concentration of the copper ions of the composition for copper etching was not reached.
  • Table 3 shows the composition of the hydrogen peroxide-based metal etching compositions according to Examples and Comparative Examples.
  • A-1 imino diacetic acid
  • A-2 glycine
  • A-3 nitrilotriacetic acid
  • B-1 methanesulfonic acid
  • B-2 ammonium persulfate
  • C-1 hydroxyethylidene diphosphonic acid
  • C-2 methylenediphosphonic acid
  • C-3 aminotris (methylenephosphonic acid)
  • D-1 pyrrole
  • D-2 pyridine.
  • Comparative Examples 11 and 12 only the first subchelating agent, which is a sulfuric acid subchelating agent, is included as the subchelating agent, and in Comparative Examples 13 to 15, a phosphoric acid subchelating agent is used as the subchelating agent. It is the case containing only 2 subchelating agents.
  • Comparative Example 16 the same kind of first and second subchelating agents as in Example were used, but nitrilotriacetic acid was used as the main chelating agent.
  • Comparative Example 17 the first subchelating agent and the second subchelating agent were mixed at a weight ratio of 6: 4, but at this time, the second subchelating agent used a compound containing a tertiary amino group.
  • Comparative Example 18 a first subchelating agent and a second subchelating agent of the same kind as in Example were used, but pyridine was used as an etching inhibitor.
  • Table 4 shows the extent to which the characteristics of the metal etching composition changes over time according to the components of the hydrogen peroxide-based metal etching composition having the composition shown in Table 3.
  • the experimental temperature was room temperature and evaluated at 25 ° C. and 30 ° C. in consideration of seasonal characteristics. In addition, since the metal etching composition is usually used within 30 days from the production date, the change in properties up to 30 days was observed.
  • the degree of perhydrolysis was a change relative to the initial concentration of hydrogen peroxide, measured by potassium permanganate (KmnO 4 ) titration, and calculated according to Equation 1 below.
  • Component denaturation is a change relative to the concentration of the initial additives (first sub chelating agent and second sub chelating agent), the content of the first sub chelating agent and the second sub chelating agent by IC-ion analysis method, respectively, Calculated according to Eq.
  • EPD End Point Detection
  • Example 9 25 -1.0 -2.5 0 -0.5 -1.0 +1.0 30 -2.6 -8.7 -0.4 -0.8 +0.8 +7.0
  • Example 10 25 -1.0 -3.0 0 -0.5 0 +1.0 30 -2.7 -9.0 -0.5 -0.7 +1.0 +7.5
  • Example 11 25 -1.1 -3.2 0 -0.5 +0.5 +1.0 30 -2.7 -9.1 -0.5 -0.85 +1.0 +8.1
  • Example 12 25 -1.2 -3.5 0 -0.45 +0.5 +1.0 30 -3.3 -9.2 -0.5 -0.8 +1.2 +7.9
  • Example 13 25 -1.0 -3.5 0 -0.5 +0.5 +1.5 30 -2.9 -9.5 -0.5 -0.9 +1.5 +9.3 Comparative Example 11 25 -1.5 -5.1 0 -0.65 +1.0 +3.8 30 -4.5 -16.0 -0.5
  • Table 5 shows the extent to which the characteristics of the metal etching composition changes over time during etching using the hydrogen peroxide-based metal etching composition having the composition shown in Table 3.
  • the experimental temperature is 33 ° C., which is a typical etching temperature, and all evaluation values are 0 ppm, i.e., 2,500 ppm of copper powder is added into the metal etching composition based on the value measured without adding copper powder into the metal etching composition.
  • the degree of change when the copper powder of 5,000 ppm and when added.
  • Comparative Example 15 the degree of perhydrolysis, component denaturation and EPD change was significantly higher than that of Comparative Examples 11 to 14, which is aminotris (methylene) which is the second subchelating agent used in Comparative Example 15. Phosphonic acid) is expected to result from reaction with hydrogen peroxide to form N-oxide.
  • nitrilotriacetic acid, aminotris (methylenephosphonic acid) and pyridine are used as materials capable of reacting with hydrogen peroxide to form N-oxide, respectively.
  • hydrogen peroxide and the compound react with each other to form N-oxide it was confirmed that the degree of perhydrolysis, component denaturation and EPD change increased.

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Abstract

La présente invention concerne : une composition pour la gravure de cuivre; et une composition à base de peroxyde d'hydrogène pour la gravure de métal et, plus particulièrement : une composition pour la gravure de cuivre pouvant empêcher la formation d'un précipité de cuivre par augmentation de la stabilité d'une liaison de chélate formée entre le cuivre et la matière organique; et une composition à base de peroxyde d'hydrogène pour la gravure de métal pouvant empêcher la décomposition du peroxyde d'hydrogène et la dégénérescence des autres composants qu'elle contient.
PCT/KR2016/013412 2015-11-19 2016-11-21 Composition pour la gravure de cuivre, et composition à base de peroxyde d'hydrogène pour la gravure de métal Ceased WO2017086758A1 (fr)

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CN112064032B (zh) * 2020-09-11 2022-04-01 武汉迪赛新材料有限公司 一种能提高过氧化氢系蚀刻液使用寿命的补充液
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