CN112981405B - 一种钛钨蚀刻液及其制备方法和应用 - Google Patents
一种钛钨蚀刻液及其制备方法和应用 Download PDFInfo
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- 238000005530 etching Methods 0.000 title claims abstract description 91
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000008139 complexing agent Substances 0.000 claims abstract description 21
- 239000003381 stabilizer Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000004310 lactic acid Substances 0.000 claims description 7
- 235000014655 lactic acid Nutrition 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 2
- 229960001231 choline Drugs 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
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- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 24
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- 238000005260 corrosion Methods 0.000 abstract description 13
- 238000012360 testing method Methods 0.000 description 26
- 239000010949 copper Substances 0.000 description 22
- 239000010931 gold Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 229910001080 W alloy Inorganic materials 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 239000004220 glutamic acid Substances 0.000 description 3
- 235000013922 glutamic acid Nutrition 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910001922 gold oxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012858 packaging process Methods 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
- H01L21/76865—Selective removal of parts of the layer
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Abstract
本发明提供了一种钛钨蚀刻液及其制备方法和应用,所述钛钨蚀刻液以重量份数计包括过氧化氢15‑30份、金属络合剂0.1‑20份、过氧化氢稳定剂0.1‑10份、pH调节剂0.1‑20份和水。本发明提供的钛钨蚀刻液蚀刻效果好,对底材无腐蚀,稳定性好,使用寿命长。
Description
技术领域
本发明属于半导体制备领域,具体涉及一种钛钨蚀刻液及其制备方法和应用,尤其涉及一种蚀刻效果好的钛钨蚀刻液及其制备方法和应用。
背景技术
近年来,铜或金凸块技术是新一代芯片互连技术,用于集成电路封装工艺过程芯片和基板的连接,相较于传统的焊料凸块封装工艺,具有更优的导电性能、热性能和可靠性,对电迁移有更好的抵抗力,更适用于细间距使互连密度更大、成本低等优点。在凸块制造过程中,由于铜或金与二氧化硅/硅的粘附力不佳,因此需要在铜或金与二氧化硅/硅之间布上钛(Ti)或钛钨(TiW)作为粘附层,然后溅射铜作为电镀种子层,从而形成凸块下金属化层(UBM)作为凸块电镀时的导电层。凸块电镀完成后,须将基板上非图形区域内多余的凸块下金属化(UBM)层蚀刻掉,而不影响基板上图形区域内的凸块及凸块下的金属化(UBM)层。一般是分步蚀刻,先将UBM上层的铜种子层蚀刻去除,再将裸露出的下层钛(Ti)或钛钨(TiW)粘附层蚀刻去除。
目前市面上使用的钛钨(TiW)蚀刻液一般是含有氢氟酸或同时含有硝酸或醋酸或磷酸的强酸性蚀刻液、过氧化氢和无机酸(例如氢氟酸)或有机酸的混合物或过氧化氢和氨或其它碱的混合物。含氟的酸性蚀刻液存在侵蚀硅和二氧化硅等基板,腐蚀Cu、Al等底材的问题;而含过氧化氢的碱性蚀刻液存在过氧化氢分解快、蚀刻速率慢或蚀刻速率变化大、蚀刻稳定性差、选择性差、使用寿命短等问题。
CN108130535B公开了一种钛钨合金的蚀刻液,所述钛钨合金的蚀刻液包含a)10-32重量百分比的氧化剂、b)1.32-6.78重量百分比的pH调整剂、c)0.1-14重量百分比的铜腐蚀抑制剂、d)2-14重量百分比的pH缓冲剂及e)35-66重量百分比的水。该发明是通过将pH缓冲剂加入于钛钨合金的蚀刻液中,使得在钛钨合金的蚀刻期间可以有效地减缓蚀刻液pH值的降低,故蚀刻液不会因为pH值的降低而腐蚀铜金属。
由于目前市面上使用的钛钨蚀刻液含有强腐蚀物质,对底材存在较大腐蚀,同时稳定性低。因此,如何提供一种不伤底材、稳定性好、使用寿命长的钛钨蚀刻液,成为了亟待解决的问题。
发明内容
针对现有技术的不足,本发明的目的在于提供一种钛钨蚀刻液及其制备方法和应用,尤其提供一种蚀刻效果好的钛钨蚀刻液及其制备方法和应用。本发明提供的钛钨蚀刻液蚀刻效果好,对底材无腐蚀,稳定性好,使用寿命长。
为达到此发明目的,本发明采用以下技术方案:
第一方面,本发明提供了一种钛钨蚀刻液,所述钛钨蚀刻液以重量份数计包括过氧化氢15-30份、金属络合剂0.1-20份、过氧化氢稳定剂0.1-10份、pH调节剂0.1-20份和水。
其中,过氧化氢的份数可以是15份、16份、17份、18份、19份、20份、21份、22份、23份、24份、25份、26份、27份、28份、29份或30份等,金属络合剂的份数可以是0.1份、0.5份、1份、2份、3份、4份、5份、6份、7份、8份、9份、10份、11份、12份、13份、14份、15份、16份、17份、18份、19份或20份等,过氧化氢稳定剂的份数可以是0.1份、0.5份、1份、2份、3份、4份、5份、6份、7份、8份、9份或10份等,pH调节剂的份数可以是0.1份、0.5份、1份、2份、3份、4份、5份、6份、7份、8份、9份、10份、11份、12份、13份、14份、15份、16份、17份、18份、19份或20份等,但不限于以上所列举的数值,上述数值范围内其他未列举的数值同样适用。
上述特定组分及配比的钛钨蚀刻液蚀刻效果好,对底材无腐蚀,稳定性好,使用寿命长;通过金属络合剂与过氧化氢稳定剂二者协同增效,提高了所述钛钨蚀刻液的稳定性;采用金属络合剂保护了底材,避免了所述钛钨蚀刻液对底材的腐蚀;同时组成中不含氢氟酸,避免了对底材的腐蚀和对环境的污染。
优选地,所述钛钨蚀刻液以重量份数计包括过氧化氢20-27份、金属络合剂5-15份、过氧化氢稳定剂2-7份、pH调节剂2-10份和水。
上述特定组分及配比进一步提高了所述钛钨蚀刻液的蚀刻效果和稳定性。
优选地,所述金属络合剂包括乙醇酸、乳酸、草酸、丙二酸、琥珀酸、苹果酸、谷氨酸、亚氨基二乙酸、二乙烯三胺五乙酸、乙二胺四乙酸、聚天冬氨酸、苯丙氨酸、牛磺酸、扁桃酸、二甘醇酸中任意一种或至少两种的组合,例如乙醇酸和乳酸的组合、乳酸和草酸的组合或丙二酸和谷氨酸的组合等,但不限于以上所列举的组合,上述组合范围内其他未列举的组合同样适用。
上述特定金属络合剂能够保护底材不被腐蚀,同时与过氧化氢稳定剂协同作用,提高了所述钛钨蚀刻液的稳定性。
优选地,所述金属络合剂包括乳酸和草酸的组合、丙二酸和琥珀酸的组合或谷氨酸和琥珀酸的组合中任意一种,优选乳酸和草酸的组合。
上述特定金属络合剂的组合进一步提高了所述金属络合剂对提高所述钛钨蚀刻液的稳定性的作用。
优选地,所述过氧化氢稳定剂包括乙二醇、脂肪醇聚氧乙烯醚、二乙二醇、三乙二醇或乙二醇单丁醚中任意一种或至少两种的组合,例如乙二醇和乙二醇单丁醚的组合、乙二醇和脂肪醇聚氧乙烯醚的组合或二乙二醇和三乙二醇的组合等,但不限于以上所列举的组合,上述组合范围内其他未列举的组合同样适用,优选乙二醇和乙二醇单丁醚的组合。
上述特定过氧化氢稳定剂及其组合能够与金属络合剂协同作用,提高所述钛钨蚀刻液的稳定性。
优选地,所述pH调节剂包括磷酸、硫酸、磷酸二氢钠、磷酸氢二钠、焦磷酸钠、磷酸二氢铵、磷酸氢二铵、磷酸铵、硫酸氢铵、硫酸氢钠、硫酸氢钾、乙酸铵、草酸铵、柠檬酸铵、氨、胆碱或二氮杂二环中任意一种或至少两种的组合,例如磷酸和磷酸铵的组合、硫酸和硫酸氢铵的组合或磷酸二氢铵和磷酸氢二铵的组合等,但不限于以上所列举的组合,上述组合范围内其他未列举的组合同样适用。
优选地,所述钛钨蚀刻液的pH为3-8,例如3、4、5、6、7或8等,但不限于以上所列举的数值,上述数值范围内其他未列举的数值同样适用。
优选地,所述钛钨蚀刻液的pH为3-5。
第二方面,本发明提供了如上所述的钛钨蚀刻液的制备方法,所述制备方法包括以下步骤:将过氧化氢、金属络合剂、过氧化氢稳定剂、pH调节剂和水混合,得到所述钛钨蚀刻液。
第三方面,本发明还提供了如上所述的钛钨蚀刻液在凸块制程中的应用。
相对于现有技术,本发明具有以下有益效果:
本发明通过选择特定组分及配比制备得到了一种钛钨蚀刻液,其具有蚀刻效果好、对底材无腐蚀、稳定性好、使用寿命长的特点;通过金属络合剂与过氧化氢稳定剂二者协同增效,提高了所述钛钨蚀刻液的稳定性;采用金属络合剂保护了底材,避免了所述钛钨蚀刻液对底材的腐蚀;同时组成中不含氢氟酸,避免了对底材的腐蚀和对环境的污染。
附图说明
图1是Cu凸块试片TiW层处理前显微照片;
图2是Au凸块试片TiW层处理前显微照片;
图3是实施例15提供的钛钨蚀刻液处理后的Cu凸块试片TiW层的显微照片;
图4是实施例15提供的钛钨蚀刻液处理后的Au凸块试片TiW层的显微照片;
图5是对比例4提供的钛钨蚀刻液处理后的Cu凸块试片TiW层的显微照片;
图6是对比例4提供的钛钨蚀刻液处理后的Au凸块试片TiW层的显微照片。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
以下测试中的Cu凸块试片和Au凸块试片均由商业获得,其中Cu凸块试片中Cu层厚度为5000A,TIW厚度为3000A,Au凸块试片中Au层厚度为500A,TIW厚度为1000A。
实施例1-15和对比例1-4提供的钛钨蚀刻液的组成及配比如下:
实施例1提供的钛钨蚀刻液的制备方法如下:将过氧化氢、金属络合剂、过氧化氢稳定剂、pH调节剂和水混合,得到所述钛钨蚀刻液。
实施例2-15和对比例1-4提供的钛钨蚀刻液的制备方法参考实施例1。
蚀刻效果测试:
首先使用铜/金刻蚀液将Cu凸块试片和Au凸块试片的种子层的Cu/Au蚀刻掉,接着将Cu凸块试片和Au凸块试片在35℃下分别用实施例1-15和对比例1-4提供的钛钨蚀刻液浸泡,待TiW层蚀刻完全后取出,试片淋洗吹干,用显微镜观察试片表面,结果如下表和图1-6所示,其中图1、图2分别为Cu凸块试片TiW层和Au凸块试片TiW层的处理前显微照片,图3、图4分别为实施例15提供的钛钨蚀刻液处理后的Cu凸块试片TiW层和Au凸块试片TiW层的显微照片,图5、图6分别为对比例4提供的钛钨蚀刻液处理后的Cu凸块试片TiW层和Au凸块试片TiW层的显微照片:
Cu凸块TiW残留 | Au凸块TiW残留 | Cu底材腐蚀 | 基板腐蚀 | |
实施例1 | ◎ | ◎ | ◎ | ND |
实施例2 | ◎ | ◎ | ○ | ND |
实施例3 | ○ | ○ | □ | ND |
实施例4 | ◎ | ◎ | □ | ND |
实施例5 | ○ | □ | □ | ND |
实施例6 | ○ | □ | △ | ND |
实施例7 | ◎ | ◎ | ○ | ND |
实施例8 | ◎ | ◎ | □ | ND |
实施例9 | ◎ | ◎ | ○ | ND |
实施例10 | ◎ | ◎ | ○ | ND |
实施例11 | ○ | ○ | □ | ND |
实施例12 | ○ | ○ | △ | ND |
实施例13 | ◎ | ◎ | ○ | ND |
实施例14 | ◎ | ○ | ◎ | ND |
实施例15 | ◎ | ◎ | □ | ND |
对比例1 | × | × | × | ND |
对比例2 | □ | △ | △ | ND |
对比例3 | × | × | × | ND |
对比例4 | × | × | × | × |
其中,◎表示无TiW残留,○表示无明显TiW残留,□表示TiW残留较少,△表示TiW残留明显,×表示TiW大量残留或基板腐蚀严重,ND表示未检出。
从以上结果可以得出,本发明提供的钛钨蚀刻液具有蚀刻效果好、对底材无腐蚀的特点;通过比较实施例2-6可以发现,在本发明优选的范围内,所述钛钨蚀刻液蚀刻效果进一步提高。
通过比较图3-6可以发现,本发明提供的钛钨蚀刻液相比本发明保护范围外的钛钨蚀刻液,蚀刻效果更好,同时对底材无腐蚀。
稳定性测试:
对实施例1-15和对比例1-4提供的钛钨蚀刻液进行稳定性测试,将蚀刻液按照比例配制好后,保持在35℃下放置48h,每24h以上述蚀刻效果测试中的方法测试所述钛钨蚀刻液蚀刻效果,观察底材有无腐蚀,并与上述蚀刻效果测试中的结果进行比较,若蚀刻效果不发生变化,则记为√,无明显变化,则记为○,有明显变化,则记为×,结果如下:
以上结果表明,本发明通过金属络合剂与过氧化氢稳定剂复配,两者协同增效,提高了所述钛钨蚀刻液的稳定性和使用寿命。
申请人声明,本发明通过上述实施例来说明本发明的钛钨蚀刻液及其制备方法和应用,但本发明并不局限于上述实施例,即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。
另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合,为了避免不必要的重复,本发明对各种可能的组合方式不再另行说明。
Claims (6)
1.一种用于凸块制造中的钛钨蚀刻液,其特征在于,所述钛钨蚀刻液以质量分数计为过氧化氢25%、金属络合剂10%、过氧化氢稳定剂5%、pH调节剂5%和水余量;
所述金属络合剂为乳酸和草酸的组合;
所述过氧化氢稳定剂为乙二醇和乙二醇单丁醚的组合;
所述乳酸和草酸在钛钨蚀刻液中的质量分数分别为5%;
所述为乙二醇和乙二醇单丁醚在钛钨蚀刻液中的质量分数分别为2.5%。
2.根据权利要求1所述的钛钨蚀刻液,其特征在于,所述pH调节剂为磷酸、硫酸、磷酸二氢钠、磷酸氢二钠、焦磷酸钠、磷酸二氢铵、磷酸氢二铵、磷酸铵、硫酸氢铵、硫酸氢钠、硫酸氢钾、乙酸铵、草酸铵、柠檬酸铵、氨、胆碱或二氮杂二环中任意一种或至少两种的组合。
3.根据权利要求1所述的钛钨蚀刻液,其特征在于,所述钛钨蚀刻液的pH为3-8。
4.根据权利要求1所述的钛钨蚀刻液,其特征在于,所述钛钨蚀刻液的pH为3-5。
5.一种根据权利要求1-4中任一项所述的钛钨蚀刻液的制备方法,其特征在于,所述制备方法包括以下步骤:将过氧化氢、金属络合剂、过氧化氢稳定剂、pH调节剂和水混合,得到所述钛钨蚀刻液。
6.一种根据权利要求1-4中任一项所述的钛钨蚀刻液在凸块制程中的应用。
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