CN107208280A - 蚀刻液及蚀刻方法 - Google Patents
蚀刻液及蚀刻方法 Download PDFInfo
- Publication number
- CN107208280A CN107208280A CN201680007726.5A CN201680007726A CN107208280A CN 107208280 A CN107208280 A CN 107208280A CN 201680007726 A CN201680007726 A CN 201680007726A CN 107208280 A CN107208280 A CN 107208280A
- Authority
- CN
- China
- Prior art keywords
- etching solution
- acid
- weight
- group
- titanium
- 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.)
- Granted
Links
- 238000005530 etching Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010936 titanium Substances 0.000 claims abstract description 25
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003568 thioethers Chemical class 0.000 claims abstract description 8
- 125000005323 thioketone group Chemical group 0.000 claims abstract description 8
- -1 compound organosulfur compound Chemical class 0.000 claims abstract description 4
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims abstract description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 6
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 3
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-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
- GGLZPLKKBSSKCX-YFKPBYRVSA-N L-ethionine Chemical compound CCSCC[C@H](N)C(O)=O GGLZPLKKBSSKCX-YFKPBYRVSA-N 0.000 claims description 3
- 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 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- CAOMCZAIALVUPA-UHFFFAOYSA-N 3-(methylthio)propionic acid Chemical compound CSCCC(O)=O CAOMCZAIALVUPA-UHFFFAOYSA-N 0.000 claims description 2
- AQGDXJQRVOCUQX-UHFFFAOYSA-N N.[S] Chemical compound N.[S] AQGDXJQRVOCUQX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 230000001988 toxicity Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 229930182817 methionine Natural products 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000003585 thioureas Chemical class 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000005516 engineering process 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
- 239000000463 material Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 238000013112 stability test Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water 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
Landscapes
- 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)
Abstract
本发明的目的在于提供一种蚀刻液及使用该蚀刻液的蚀刻方法，所述蚀刻液可在铜的存在下选择性地蚀刻钛，而且毒性低，保存稳定性优异。本发明的蚀刻液含有选自由硫酸、盐酸及三氯乙酸所组成的群组中的至少一种酸与选自由硫酮系化合物及硫醚系化合物所组成的群组中的至少一种有机硫化合物，可在铜的存在下选择性地蚀刻钛。
Description
技术领域
本发明涉及一种用来在铜的存在下选择性地蚀刻钛的蚀刻液及使用该蚀刻液的蚀刻方法。
背景技术
以往，在蚀刻钛时一直使用含有氢氟酸或过氧化氢的蚀刻液。例如专利文献1中提出了一种钛的蚀刻液，该钛的蚀刻液是用来在铜或铝的存在下蚀刻钛，并且该蚀刻液的特征在于：利用由10重量％至40重量％的过氧化氢、0.05重量％至5重量％的磷酸、0.001重量％至0.1重量％的膦酸系化合物及氨所构成的水溶液将pH值调整为7至9。
但是，含有氢氟酸的蚀刻液存在毒性高的问题，含有过氧化氢的蚀刻液存在缺乏保存稳定性的问题。
现有技术文献
专利文献
专利文献1：日本特许第4471094号说明书。
发明内容
发明所要解决的问题
本发明是鉴于所述实际情况而成，其目的在于提供一种蚀刻液及使用该蚀刻液的蚀刻方法，所述蚀刻液可在铜的存在下选择性地蚀刻钛，而且毒性低，保存稳定性优异。
解决问题的技术手段
本发明的蚀刻液是为了在铜的存在下选择性地蚀刻钛而使用，并且含有：选自由硫酸、盐酸及三氯乙酸所组成的群组中的至少一种酸；以及选自由硫酮系化合物及硫醚系化合物所组成的群组中的至少一种有机硫化合物。
所述硫酮系化合物优选为选自由硫脲、二乙基硫脲及三甲基硫脲所组成的群组中的至少一种。
所述硫醚系化合物优选为选自由甲硫氨酸、乙硫氨酸及3-(甲硫基)丙酸所组成的群组中的至少一种。
本发明的蚀刻液优选进一步含有α-羟基羧酸和/或其盐。
所述α-羟基羧酸优选为选自由酒石酸、苹果酸、柠檬酸、乳酸及甘油酸所组成的群组中的至少一种。
优选为，所述酸的浓度为20重量％至70重量％，所述有机硫化合物的浓度为0.01重量％至10重量％。另外，所述α-羟基羧酸和/或其盐的浓度优选为0.2重量％至5重量％。
另外，本发明涉及一种使用所述蚀刻液在铜的存在下选择性地蚀刻钛的蚀刻方法。
发明的效果
本发明的蚀刻液可在铜的存在下选择性地蚀刻钛。另外，本发明的蚀刻液实质上不含氢氟酸及过氧化氢，因此毒性低，保存稳定性优异。
具体实施方式
本发明的蚀刻液为含有选自由硫酸、盐酸及三氯乙酸所组成的群组中的至少一种酸与选自由硫酮系化合物及硫醚系化合物所组成的群组中的至少一种有机硫化合物的水溶液。
所述酸中，从蚀刻速度的稳定性及酸的低挥发性的观点来看，优选为硫酸。
酸的浓度并无特别限制，优选为20重量％至70重量％，更优选为30重量％至60重量％。在酸的浓度小于20重量％的情况下，有无法获得充分的钛蚀刻速度的倾向，在超过70重量％的情况下，有蚀刻液的安全性成问题的倾向。
所述有机硫化合物具有作为还原剂及络合剂(chelate)的效果。
作为所述硫酮系化合物，例如可举出硫脲、N-烷基硫脲、N,N-二烷基硫脲、N,N'-二烷基硫脲、N,N,N'-三烷基硫脲、N,N,N',N'-四烷基硫脲、N-苯基硫脲、N,N-二苯基硫脲、N,N'-二苯基硫脲及亚乙基硫脲等。烷基硫脲的烷基并无特别限制，优选为碳数1至4的烷基。这些硫酮系化合物中，优选使用选自由作为还原剂或络合剂的效果及水溶性优异的硫脲、二乙基硫脲及三甲基硫脲所组成的群组中的至少一种。
作为所述硫醚系化合物，例如可举出甲硫氨酸、甲硫氨酸烷基酯盐酸盐、乙硫氨酸、2-羟基-4-(烷硫基)丁酸及3-(烷硫基)丙酸等。烷基的碳数并无特别限制，优选为碳数1至4。另外，这些化合物的一部分也可经取代为氢原子、羟基或氨基等其他基。这些硫醚系化合物中，优选为使用选自由作为还原剂或络合剂的效果优异的甲硫氨酸、乙硫氨酸及3-(甲硫基)丙酸所组成的群组中的至少一种。
有机硫化合物的浓度并无特别限制，优选为0.01重量％至10重量％，更优选为0.2重量％至5重量％。在有机硫化合物的浓度小于0.01重量％的情况下，无法获得充分的还原性及络合效果，有钛的蚀刻速度变得不充分的倾向，若超过10重量％则有达到溶解极限的倾向。
蚀刻液也可含有α-羟基羧酸和/或其盐。α-羟基羧酸及其盐具有作为钛的络合剂的效果，可抑制蚀刻液中产生钛的沉淀。作为所述α-羟基羧酸，例如可举出酒石酸、苹果酸、柠檬酸、乳酸及甘油酸等。
α-羟基羧酸和/或其盐的浓度并无特别限制，从络合效果及溶解性的观点来看，优选为0.2重量％至5重量％，更优选为0.5重量％至2重量％。
另外，蚀刻液也可含有亚硫酸及/或其盐。亚硫酸及其盐具有作为还原剂的效果，可提高钛的蚀刻速度。
亚硫酸和/或其盐的浓度并无特别限制，从还原性及臭气的观点来看，优选为0.02重量％至0.5重量％，更优选为0.05重量％至0.2重量％。
蚀刻液中除了上述的成分以外，也能以不妨碍本发明效果的程度添加其他成分。作为其他成分，例如可举出表面活性剂、成分稳定剂及消泡剂等。
蚀刻液可通过使所述各成分溶解于水中而容易地制备。作为所述水，优选为将离子性物质及杂质除去的水，例如优选为离子交换水、纯水、超纯水等。
蚀刻液可在使用时将各成分以成为预定浓度的方式调配，也可预先制备浓缩液并在即将使用之前稀释而使用。
使用本发明的蚀刻液的钛的蚀刻方法并无特别限制，例如可举出：对含有铜及钛的对象物涂布或喷雾蚀刻液的方法；将含有铜及钛的对象物浸渍在蚀刻液中的方法等。处理温度并无特别限制，从蚀刻速度及安全性的观点来看，优选为40℃至70℃，更优选为45℃至55℃。处理时间视对象物的表面状态及形状等而变化，通常为30秒至120秒左右。
实施例
然后，对本发明的实施例与比较例一起进行说明。此外，本发明并非限定于下述实施例而解释。
制备表1及表2所示的组成的各蚀刻液，在下述条件下进行蚀刻试验及蚀刻液的稳定性试验。此外，表1及表2所示的组成的各蚀刻液中，剩余部分为离子交换水。另外，表1及表2所示的盐酸的浓度为以氯化氢计的浓度。
(蚀刻试验)
通过溅镀法在树脂上形成50nm的钛膜，然后成膜200nm的铜膜，进而通过电镀铜在该铜膜上形成图案，将所得的基板用作试样。使用铜的蚀刻液，将试样的溅镀铜膜溶解而使钛膜露出。然后，将试样浸渍在实施例1至实施例12及比较例1至比较例3的蚀刻液中进行蚀刻实验。将实验结果示于表1。
[表1]
像表1所示那样，本发明的蚀刻液可在不蚀刻铜的情况下选择性地蚀刻钛。
(蚀刻液的稳定性试验)
将实施例1、实施例7、实施例12及比较例4的蚀刻液在室温下放置2天后，进行所述蚀刻试验，比较放置前后的蚀刻速度。将比较结果示于表2。
[表2]
像表2所示那样，本发明的蚀刻液的保存稳定性优异，即便在长期保存的情况下也可稳定地选择性地蚀刻钛。
Claims (8)
1.一种蚀刻液，其特征在于，用来在铜的存在下选择性地蚀刻钛，并且含有：
选自由硫酸、盐酸及三氯乙酸所组成的群组中的至少一种酸；以及
选自由硫酮系化合物及硫醚系化合物所组成的群组中的至少一种有机硫化合物。
2.根据权利要求1所述的蚀刻液，其特征在于，所述硫酮系化合物为选自由硫脲、二乙基硫脲及三甲基硫脲所组成的群组中的至少一种。
3.根据权利要求1或2所述的蚀刻液，其特征在于，所述硫醚系化合物为选自由甲硫氨酸、乙硫氨酸及3-(甲硫基)丙酸所组成的群组中的至少一种。
4.根据权利要求1至3中任一项所述的蚀刻液，其特征在于，进一步含有α-羟基羧酸和/或α-羟基羧酸的盐。
5.根据权利要求4所述的蚀刻液，其特征在于，所述α-羟基羧酸为选自由酒石酸、苹果酸、柠檬酸、乳酸及甘油酸所组成的群组中的至少一种。
6.根据权利要求1至5中任一项所述的蚀刻液，其特征在于，所述酸的浓度为20重量％至70重量％；
所述有机硫化合物的浓度为0.01重量％至10重量％。
7.根据权利要求4至6中任一项所述的蚀刻液，其特征在于，所述α-羟基羧酸和/或α-羟基羧酸的盐的浓度为0.2重量％至5重量％。
8.一种蚀刻方法，其特征在于，使用根据权利要求1至7中任一项所述的蚀刻液，在铜的存在下选择性地蚀刻钛。
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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107208280A true CN107208280A (zh) | 2017-09-26 |
| CN107208280B CN107208280B (zh) | 2019-06-07 |
Family
ID=56615169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680007726.5A Active CN107208280B (zh) | 2015-02-12 | 2016-01-21 | 蚀刻液及蚀刻方法 |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US20180044801A1 (zh) |
| EP (1) | EP3257969B1 (zh) |
| JP (1) | JP6429079B2 (zh) |
| KR (1) | KR102442989B1 (zh) |
| CN (1) | CN107208280B (zh) |
| TW (1) | TWI680210B (zh) |
| WO (1) | WO2016129352A1 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114196956A (zh) * | 2020-09-18 | 2022-03-18 | 珠海市丹尼尔电子科技有限公司 | 一种用于钛的蚀刻液 |
| CN115491677A (zh) * | 2022-09-22 | 2022-12-20 | 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 |
Families Citing this family (3)
| 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 |
| 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 |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3888778A (en) * | 1973-03-13 | 1975-06-10 | Merton Beckwith | Bright dip composition for tin/lead |
| US4004956A (en) * | 1974-08-14 | 1977-01-25 | Enthone, Incorporated | Selectively stripping tin or tin-lead alloys from copper substrates |
| US4588471A (en) * | 1985-03-25 | 1986-05-13 | International Business Machines Corporation | Process for etching composite chrome layers |
| US6284309B1 (en) * | 1997-12-19 | 2001-09-04 | Atotech Deutschland Gmbh | Method of producing copper surfaces for improved bonding, compositions used therein and articles made therefrom |
| US20030150840A1 (en) * | 2002-02-11 | 2003-08-14 | Gould Electronics Inc. | Etching solution for forming an embedded resistor |
| CN101153395A (zh) * | 2006-09-25 | 2008-04-02 | Mec株式会社 | 金属除去液及使用该金属除去液的金属除去方法 |
| CN101210343A (zh) * | 2006-12-29 | 2008-07-02 | 佛山市顺德区汉达精密电子科技有限公司 | 一种不锈钢电解蚀刻工艺 |
| JP2009512194A (ja) * | 2005-10-05 | 2009-03-19 | アドバンスド テクノロジー マテリアルズ，インコーポレイテッド | ポストエッチング残渣を除去するための酸化性水性洗浄剤 |
| JP2013135039A (ja) * | 2011-12-26 | 2013-07-08 | Mec Co Ltd | 配線形成方法およびエッチング液 |
| CN103789779A (zh) * | 2014-02-24 | 2014-05-14 | 昆山苏杭电路板有限公司 | 化学镀金板非沉铜孔内防金沉积工艺及其除钯处理液 |
| JP2014103179A (ja) * | 2012-11-16 | 2014-06-05 | Fujifilm Corp | 半導体基板のエッチング液、これを用いたエッチング方法及び半導体素子の製造方法 |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4180469A (en) * | 1977-12-30 | 1979-12-25 | Amchem Products, Inc. | Dithiocarbamate sulfonium salt inhibitor composition |
| JPS61266582A (ja) * | 1985-05-22 | 1986-11-26 | Okuno Seiyaku Kogyo Kk | 錫又は錫合金の剥離液 |
| US4657632A (en) * | 1985-08-29 | 1987-04-14 | Techno Instruments Investments 1983 Ltd. | Use of immersion tin coating as etch resist |
| JPS63161178A (ja) * | 1986-12-23 | 1988-07-04 | Metsuku Kk | スズまたはスズ合金の剥離液 |
| JPH06280056A (ja) * | 1993-03-30 | 1994-10-04 | Okuno Chem Ind Co Ltd | スズ又はスズ合金皮膜用剥離剤 |
| US6103627A (en) * | 1996-02-21 | 2000-08-15 | Micron Technology, Inc. | Treatment of a surface having an exposed silicon/silica interface |
| JP4401550B2 (ja) * | 2000-08-31 | 2010-01-20 | 株式会社大和化成研究所 | パラジウム又はパラジウム化合物の溶解処理方法 |
| JP4267331B2 (ja) * | 2003-01-14 | 2009-05-27 | 株式会社荏原製作所 | 基板の処理方法及びエッチング液 |
| JP4471094B2 (ja) | 2004-05-11 | 2010-06-02 | 三菱瓦斯化学株式会社 | チタンまたはチタン合金のエッチング液 |
| KR20060108436A (ko) * | 2005-04-13 | 2006-10-18 | 매그나칩 반도체 유한회사 | 반도체 소자 세정용 조성물 및 이를 이용한 반도체 소자의세정 방법 |
| KR100734274B1 (ko) * | 2005-09-05 | 2007-07-02 | 삼성전자주식회사 | 기판 세정용 조성물을 이용한 게이트 형성 방법 |
| WO2012048079A2 (en) * | 2010-10-06 | 2012-04-12 | Advanced Technology Materials, Inc. | Composition and process for selectively etching metal nitrides |
| KR101838787B1 (ko) * | 2011-06-30 | 2018-03-14 | 아사히 가세이 가부시키가이샤 | 에칭액 및 그것을 이용한 에칭 방법 |
| JP5933950B2 (ja) * | 2011-09-30 | 2016-06-15 | アドバンスド テクノロジー マテリアルズ，インコーポレイテッド | 銅または銅合金用エッチング液 |
| CN104334706A (zh) * | 2012-03-18 | 2015-02-04 | 安格斯公司 | 具有改进的阻挡层相容性和清洁性能的cpm后配制物 |
| WO2014203649A1 (ja) * | 2013-06-18 | 2014-12-24 | 株式会社Ｊｃｕ | 無電解金属めっきのブリッジ防止液およびこれを用いたプリント配線板の製造方法 |
-
2015
- 2015-02-12 JP JP2015025385A patent/JP6429079B2/ja active Active
-
2016
- 2016-01-21 KR KR1020177023507A patent/KR102442989B1/ko active IP Right Grant
- 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
- 2016-01-21 EP EP16748997.0A patent/EP3257969B1/en active Active
- 2016-01-21 CN CN201680007726.5A patent/CN107208280B/zh active Active
- 2016-02-01 TW TW105103129A patent/TWI680210B/zh active
-
2019
- 2019-12-09 US US16/707,387 patent/US20200109475A1/en not_active Abandoned
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3888778A (en) * | 1973-03-13 | 1975-06-10 | Merton Beckwith | Bright dip composition for tin/lead |
| US4004956A (en) * | 1974-08-14 | 1977-01-25 | Enthone, Incorporated | Selectively stripping tin or tin-lead alloys from copper substrates |
| US4588471A (en) * | 1985-03-25 | 1986-05-13 | International Business Machines Corporation | Process for etching composite chrome layers |
| US6284309B1 (en) * | 1997-12-19 | 2001-09-04 | Atotech Deutschland Gmbh | Method of producing copper surfaces for improved bonding, compositions used therein and articles made therefrom |
| US20030150840A1 (en) * | 2002-02-11 | 2003-08-14 | Gould Electronics Inc. | Etching solution for forming an embedded resistor |
| JP2009512194A (ja) * | 2005-10-05 | 2009-03-19 | アドバンスド テクノロジー マテリアルズ，インコーポレイテッド | ポストエッチング残渣を除去するための酸化性水性洗浄剤 |
| CN101153395A (zh) * | 2006-09-25 | 2008-04-02 | Mec株式会社 | 金属除去液及使用该金属除去液的金属除去方法 |
| CN101210343A (zh) * | 2006-12-29 | 2008-07-02 | 佛山市顺德区汉达精密电子科技有限公司 | 一种不锈钢电解蚀刻工艺 |
| JP2013135039A (ja) * | 2011-12-26 | 2013-07-08 | Mec Co Ltd | 配線形成方法およびエッチング液 |
| JP2014103179A (ja) * | 2012-11-16 | 2014-06-05 | Fujifilm Corp | 半導体基板のエッチング液、これを用いたエッチング方法及び半導体素子の製造方法 |
| CN103789779A (zh) * | 2014-02-24 | 2014-05-14 | 昆山苏杭电路板有限公司 | 化学镀金板非沉铜孔内防金沉积工艺及其除钯处理液 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114196956A (zh) * | 2020-09-18 | 2022-03-18 | 珠海市丹尼尔电子科技有限公司 | 一种用于钛的蚀刻液 |
| 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 |
| CN115491677A (zh) * | 2022-09-22 | 2022-12-20 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20180044801A1 (en) | 2018-02-15 |
| TW201634753A (zh) | 2016-10-01 |
| TWI680210B (zh) | 2019-12-21 |
| WO2016129352A1 (ja) | 2016-08-18 |
| EP3257969A1 (en) | 2017-12-20 |
| JP2016148081A (ja) | 2016-08-18 |
| EP3257969B1 (en) | 2020-04-22 |
| CN107208280B (zh) | 2019-06-07 |
| EP3257969A4 (en) | 2018-02-21 |
| KR20170117434A (ko) | 2017-10-23 |
| US20200109475A1 (en) | 2020-04-09 |
| KR102442989B1 (ko) | 2022-09-14 |
| JP6429079B2 (ja) | 2018-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107208280A (zh) | 蚀刻液及蚀刻方法 | |
| CN107075693B (zh) | 铜、钼金属层叠膜蚀刻液组合物、使用该组合物的蚀刻方法及延长该组合物的寿命的方法 | |
| CN107227463B (zh) | 铜/钼膜或铜/钼合金膜的蚀刻液组合物 | |
| CA2004796C (en) | Inhibited composition and method for stripping tin, lead or tin-lead alloy from copper surfaces | |
| CN105648440A (zh) | 液体组合物及使用其的蚀刻方法 | |
| CN104730870B (zh) | 用于除去氮化钛硬掩模和蚀刻残留物的组合物 | |
| CN105648439A (zh) | 液体组合物及使用其的蚀刻方法 | |
| US5939336A (en) | Aqueous solutions of ammonium fluoride in propylene glycol and their use in the removal of etch residues from silicon substrates | |
| WO2011093445A1 (ja) | 銅／チタン系多層薄膜用エッチング液 | |
| CN103814432B (zh) | 增大蚀刻液蚀刻用量的铜/钼合金膜的蚀刻方法 | |
| WO2018047210A1 (ja) | 多層膜用エッチング液とエッチング濃縮液およびエッチング方法 | |
| KR20060045996A (ko) | 티탄 또는 티탄 합금용 에칭액 | |
| CN111334800B (zh) | Pcb微蚀液及其制备方法 | |
| JP2009144180A (ja) | エッチング用組成物及びエッチング方法 | |
| EP0418333B1 (en) | Composition and method for stripping tin or tin-lead alloy from copper surfaces | |
| EP0083631B1 (en) | Method of preserving the solderability of copper | |
| US20060180789A1 (en) | Formulation for corrosion and scale inhibition | |
| US4233113A (en) | Dissolution of metals utilizing an aqueous H2 O2 -H2 SO4 -thioamide etchant | |
| CN114250469B (zh) | 一种蚀刻液组合物及其制备方法 | |
| JP2002069656A (ja) | パラジウム又はパラジウム化合物の溶解処理液 | |
| EP0559379A1 (en) | Composition and method for stripping tin or tin-lead alloy from copper surfaces | |
| JP3854523B2 (ja) | レジスト剥離剤 | |
| KR20210056768A (ko) | 금속막 식각액 조성물 | |
| KR20200048140A (ko) | 식각액 조성물 및 이를 이용한 금속막 식각 방법 | |
| KR20210056769A (ko) | 금속막의 식각방법 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |