US20180044801A1 - Etching liquid and etching method - Google Patents
Etching liquid and etching method Download PDFInfo
- Publication number
- US20180044801A1 US20180044801A1 US15/550,752 US201615550752A US2018044801A1 US 20180044801 A1 US20180044801 A1 US 20180044801A1 US 201615550752 A US201615550752 A US 201615550752A US 2018044801 A1 US2018044801 A1 US 2018044801A1
- Authority
- US
- United States
- Prior art keywords
- acid
- etching
- etching liquid
- group
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- 238000005530 etching Methods 0.000 title claims abstract description 84
- 239000007788 liquid Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010936 titanium Substances 0.000 claims abstract description 23
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 150000002898 organic sulfur compounds Chemical class 0.000 claims abstract description 10
- -1 thioketone compound Chemical class 0.000 claims abstract description 8
- 150000003568 thioethers Chemical class 0.000 claims abstract description 7
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 claims description 10
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 7
- 229930182817 methionine Natural products 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- CAOMCZAIALVUPA-UHFFFAOYSA-N 3-(methylthio)propionic acid Chemical compound CSCCC(O)=O CAOMCZAIALVUPA-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- GGLZPLKKBSSKCX-YFKPBYRVSA-N L-ethionine Chemical compound CCSCC[C@H](N)C(O)=O GGLZPLKKBSSKCX-YFKPBYRVSA-N 0.000 claims description 5
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 3
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 230000001988 toxicity Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 235000006109 methionine Nutrition 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004470 DL Methionine Substances 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical compound CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- FPZXQVCYHDMIIA-UHFFFAOYSA-N 1,1-diphenylthiourea Chemical compound C=1C=CC=CC=1N(C(=S)N)C1=CC=CC=C1 FPZXQVCYHDMIIA-UHFFFAOYSA-N 0.000 description 1
- JGSIAOZAXBWRFO-UHFFFAOYSA-N 3-methylsulfanyl-1-phenyl-4,5-dihydrobenzo[g]indazole Chemical compound C1CC2=CC=CC=C2C2=C1C(SC)=NN2C1=CC=CC=C1 JGSIAOZAXBWRFO-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical class CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- AQXQGFFJZVRMRY-UHFFFAOYSA-N [Cu].[Ti].[Cu].[Ti] Chemical compound [Cu].[Ti].[Cu].[Ti] AQXQGFFJZVRMRY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/108—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by semi-additive methods; masks therefor
Definitions
- the present invention relates to an etching liquid for etching titanium selectively in the presence of copper, and an etching method using this etching liquid.
- Patent Document 1 suggests an etching liquid for etching titanium in the presence of copper or aluminum, the pH of this liquid being adjusted into the range of 7 to 9 with an aqueous solution including 10 to 40% by weight of hydrogen peroxide, 0.05 to 5% by weight of phosphoric acid, 0.001 to 0.1% by weight of a phosphonic acid-based compound, and ammonia.
- the etching liquid containing hydrofluoric acid has a problem of being high in toxicity.
- the etching liquid containing hydrogen peroxide has a problem of being poor in storage stability.
- the present invention has been made, and an object thereof is to provide an etching liquid which is capable of etching titanium selectively in the presence of copper, and is further low in toxicity and excellent in storage stability; and an etching method using this etching liquid.
- the etching liquid of the present invention is used to etch titanium selectively in the presence of copper, and comprises:
- At least one acid selected from the group consisting of sulfuric acid, hydrochloric acid, and trichloroacetic acid;
- At least one organic sulfur compound selected from the group consisting of a thioketone compound and a thioether compound.
- the thioketone compound be at least one selected from the group consisting of thiourea, diethylthiourea, and trimethylthiourea.
- the thioether compound be at least one selected from the group consisting of methionine, ethionine, and 3-(methylthio)propionic acid.
- the etching liquid of the present invention preferably further comprises an ⁇ -hydroxycarboxylic acid, and/or a salt thereof.
- the ⁇ -hydroxycarboxylic acid be at least one selected from the group consisting of tartaric acid, malic acid, citric acid, lactic acid, and glyceric acid.
- the concentration of the acid(s) be from 20 to 70% by weight, and the concentration of the organic sulfur compound(s) be from 0.01 to 10% by weight.
- the concentration of the ⁇ -hydroxycarboxylic acid and/or the salt thereof is preferably from 0.2 to 5% by weight.
- the present invention also relates to an etching method, comprising etching titanium selectively in the presence of copper by using the above-mentioned etching liquid.
- the etching liquid of the present invention makes it possible to etch titanium selectively in the presence of copper. Moreover, the etching liquid of the present invention substantially contains neither hydrofluoric acid nor hydrogen peroxide to be low in toxicity and excellent in storage stability.
- the etching liquid of the present invention is an aqueous solution including at least one acid selected from the group consisting of sulfuric acid, hydrochloric acid, and trichloroacetic acid, and at least one organic sulfur compound selected from the group consisting of a thioketone compound and a thioether compound.
- sulfuric acid is preferred from the viewpoint of a low volatility of the acid, and the stability of the etching speed of the etching liquid.
- the concentration of the acid(s) in the etching liquid is not particularly limited, and is preferably from 20 to 70% by weight, more preferably from 30 to 60% by weight. If the acid concentration is less than 20% by weight, the etching liquid tends not to gain a sufficient speed of etching titanium. If the acid concentration is more than 70% by weight, the safety of the etching liquid tends to become a problem.
- the organic sulfur compound(s) has/have advantageous effects of functioning as a reductant and a chelating agent.
- Examples of the thioketone compound include thiourea, N-alkylthioureas, N,N-dialkylthioureas, N,N′-dialkylthioureas, N,N,N′-trialkylthioureas, N,N,N′,N′-tetraalkylthioureas, N-phenylthiourea, N,N-diphenylthiourea, N,N′-diphenylthiourea, and ethylenethiourea.
- the alkyl group(s) of any one of the alkylthioureas is/are not particularly limited.
- the alkyl group(s) is/are (each) preferably an alkyl group having 1 to 4 carbon atoms. It is preferred to use, out of these examples, at least one selected from the group consisting of thiourea, diethylthiourea, and trimethylthiourea, which are each excellent in advantageous effects of functioning as a reductant or chelating agent, and in water solubility.
- Examples of the thioether compound include methionine, a hydrochloride of an alkyl ester of methionine, ethionine, 2-hydroxy-4-(alkylthio) butyric acids, and 3-(alkylthio)propionic acids.
- the number of carbon atoms in each of the alkyl groups is not particularly limited, and is preferably from 1 to 4. These compounds may each be partially substituted with one or more hydrogen atoms, or one or more hydroxyl groups, amino groups or other groups.
- the concentration of the organic sulfur compound(s) in the etching liquid is not particularly limited, and is preferably from 0.01 to 10% by weight, more preferably from 0.2 to 5% by weight. If the concentration of the organic sulfur compound(s) is less than 0.01% by weight, the etching liquid can gain neither a sufficient reducing performance nor a sufficient chelating effect so that the speed of etching titanium tends to be insufficient. If the concentration is more than 10% by weight, the dissolution of the organic sulfur compound(s) in the etching liquid tends to reach a limit.
- the etching liquid may include an ⁇ -hydroxycarboxylic acid, and/or a salt thereof.
- the ⁇ -hydroxycarboxylic acid, and the salt thereof have advantageous effects of functioning as a chelating agent for titanium, and can therefore restrain the generation of any precipitation of titanium in the etching liquid.
- the ⁇ -hydroxycarboxylic acid include tartaric acid, malic acid, citric acid, lactic acid, and glyceric acid.
- the concentration of the ⁇ -hydroxycarboxylic acid and/or the salt thereof in the etching liquid is not particularly limited, and is preferably from 0.2 to 5% by weight, more preferably from 0.5 to 2% by weight from the viewpoint of the chelating effect and the solubility thereof.
- the etching liquid may include sulfurous acid and/or a sulfite thereof.
- Sulfurous acid and the sulfite thereof have advantageous effects of functioning as a reductant, and can therefore improve the speed of etching titanium.
- the concentration of sulfurous acid and/or the sulfite thereof in the etching liquid is not particularly limited, and is preferably from 0.02 to 0.5% by weight, more preferably from 0.05 to 0.2% by weight from the viewpoint of the reducing performance and odor thereof.
- any other component may be added to the etching liquid as far as the advantageous effects of the present invention are not hindered.
- the other component include a surfactant, a component stabilizer, and an antifoaming agent.
- the etching liquid can easily be prepared by dissolving the above-mentioned individual components into water.
- the water is preferably water from which ionic substances and impurities have been removed.
- the species of the water is preferably, for example, ion exchange water, pure water, and super pure water.
- the etching liquid it is allowable to blend the individual components with each other to have predetermined concentrations, respectively, when the etching liquid is used; or prepare a concentrated liquid of the etching liquid beforehand, dilute the concentrated liquid immediately before the use, and then use the diluted liquid.
- An etching method using the etching liquid of the present invention is not particularly limited. Examples of the method include a method of coating or spraying the etching liquid onto a target object containing copper and titanium, and a method of immersing a target object containing copper and titanium into the etching liquid.
- the treatment temperature is not particularly limited, and is preferably from 40 to 70° C., more preferably 45 to 55° C. from the viewpoint of the etching speed of the etching liquid, and safety.
- the treatment period is varied in accordance with, for example, the surface state and shape of the target object. The period is usually from 30 to 120 seconds.
- Each etching liquid was prepared to have one out of compositions shown in Tables 1 and 2. Under conditions described below, an etching test and an etching liquid stability test were conducted. In the etching liquid of each of the compositions shown in Tables 1 and 2, the balance thereof was made of ion exchange water. Each concentration of hydrochloric acid shown in Tables 1 and 2 is the concentration of the acid as hydrogen chloride.
- a titanium film was formed into a thickness of 50 nm onto each resin piece by sputtering, and next a copper film was formed into a thickness of 200 nm onto the titanium film. Furthermore, a pattern was formed thereon by electroless plating.
- the resultant substrate was used as each sample.
- An etching liquid for copper was used to dissolve the sputtered copper film of the sample to make the titanium film naked. Thereafter, any one of the samples was immersed in the etching liquid of each of Examples 1 to 12 and Comparative Examples 1 to 3 to make an etching test. The results are shown in Table 1.
- the etching liquid of the present invention makes it possible to etch titanium selectively without etching copper.
- the etching liquids of the present invention are excellent in storage stability, and makes it possible to etch titanium selectively even after stored over a long term.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015025385A JP6429079B2 (ja) | 2015-02-12 | 2015-02-12 | エッチング液及びエッチング方法 |
| JP2015-025385 | 2015-02-12 | ||
| PCT/JP2016/051690 WO2016129352A1 (ja) | 2015-02-12 | 2016-01-21 | エッチング液及びエッチング方法 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2016/051690 A-371-Of-International WO2016129352A1 (ja) | 2015-02-12 | 2016-01-21 | エッチング液及びエッチング方法 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US16/707,387 Division US20200109475A1 (en) | 2015-02-12 | 2019-12-09 | Etching method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20180044801A1 true US20180044801A1 (en) | 2018-02-15 |
Family
ID=56615169
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US15/550,752 Abandoned US20180044801A1 (en) | 2015-02-12 | 2016-01-21 | Etching liquid and etching method |
| US16/707,387 Abandoned US20200109475A1 (en) | 2015-02-12 | 2019-12-09 | Etching method |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US16/707,387 Abandoned US20200109475A1 (en) | 2015-02-12 | 2019-12-09 | Etching method |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US20180044801A1 (ko) |
| EP (1) | EP3257969B1 (ko) |
| JP (1) | JP6429079B2 (ko) |
| KR (1) | KR102442989B1 (ko) |
| CN (1) | CN107208280B (ko) |
| TW (1) | TWI680210B (ko) |
| WO (1) | WO2016129352A1 (ko) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116083910A (zh) * | 2022-12-28 | 2023-05-09 | 湖北兴福电子材料股份有限公司 | 一种钛或钛合金的蚀刻液 |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201930647A (zh) * | 2017-12-22 | 2019-08-01 | 德商德國艾托特克公司 | 用於選擇性移除鈀之方法及處理組合物 |
| JP7486294B2 (ja) * | 2019-09-10 | 2024-05-17 | Ｄｏｗａテクノロジー株式会社 | 洗浄液、洗浄液の製造方法及び設備の洗浄方法 |
| CN114196956B (zh) * | 2020-09-18 | 2024-03-12 | 珠海市丹尼尔电子科技有限公司 | 一种用于钛的蚀刻液 |
| CN115491677B (zh) * | 2022-09-22 | 2023-10-13 | 易安爱富(武汉)科技有限公司 | 一种钛铝钛复合膜层的酸性蚀刻液及制备方法 |
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- 2016-01-21 CN CN201680007726.5A patent/CN107208280B/zh active Active
- 2016-01-21 KR KR1020177023507A patent/KR102442989B1/ko active IP Right Grant
- 2016-01-21 EP EP16748997.0A patent/EP3257969B1/en active Active
- 2016-01-21 US US15/550,752 patent/US20180044801A1/en not_active Abandoned
- 2016-01-21 WO PCT/JP2016/051690 patent/WO2016129352A1/ja active Application Filing
- 2016-02-01 TW TW105103129A patent/TWI680210B/zh active
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| US4657632A (en) * | 1985-08-29 | 1987-04-14 | Techno Instruments Investments 1983 Ltd. | Use of immersion tin coating as etch resist |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116083910A (zh) * | 2022-12-28 | 2023-05-09 | 湖北兴福电子材料股份有限公司 | 一种钛或钛合金的蚀刻液 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20200109475A1 (en) | 2020-04-09 |
| TW201634753A (zh) | 2016-10-01 |
| CN107208280B (zh) | 2019-06-07 |
| WO2016129352A1 (ja) | 2016-08-18 |
| TWI680210B (zh) | 2019-12-21 |
| EP3257969A4 (en) | 2018-02-21 |
| JP6429079B2 (ja) | 2018-11-28 |
| KR20170117434A (ko) | 2017-10-23 |
| EP3257969B1 (en) | 2020-04-22 |
| JP2016148081A (ja) | 2016-08-18 |
| KR102442989B1 (ko) | 2022-09-14 |
| EP3257969A1 (en) | 2017-12-20 |
| CN107208280A (zh) | 2017-09-26 |
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