CN111902569B - 蚀刻液 - Google Patents
蚀刻液 Download PDFInfo
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- CN111902569B CN111902569B CN201880091665.4A CN201880091665A CN111902569B CN 111902569 B CN111902569 B CN 111902569B CN 201880091665 A CN201880091665 A CN 201880091665A CN 111902569 B CN111902569 B CN 111902569B
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- etching solution
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- etching
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- zinc oxide
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- 238000005530 etching Methods 0.000 title claims abstract description 112
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 14
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960004585 etidronic acid Drugs 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims abstract description 8
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940120146 EDTMP Drugs 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 7
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims abstract description 5
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 31
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 23
- 229910052733 gallium Inorganic materials 0.000 claims description 23
- 229910052738 indium Inorganic materials 0.000 claims description 23
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 19
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 16
- 239000011787 zinc oxide Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 230000004888 barrier function Effects 0.000 claims description 11
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- -1 amine compounds Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 34
- 238000005260 corrosion Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000011241 protective layer Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 235000010599 Verbascum thapsus Nutrition 0.000 description 3
- 244000178289 Verbascum thapsus Species 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- QMHIMXFNBOYPND-UHFFFAOYSA-N 4-methylthiazole Chemical compound CC1=CSC=N1 QMHIMXFNBOYPND-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 150000003536 tetrazoles Chemical class 0.000 description 2
- PVPTUASRAVWKGX-UHFFFAOYSA-N 1,2-dihydrotriazol-3-amine Chemical compound NN1NNC=C1 PVPTUASRAVWKGX-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 1
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000011800 void material Substances 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
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- 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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- 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
- H01L21/34—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 not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
- H01L21/46—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428
- H01L21/461—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/4763—Deposition of non-insulating, e.g. conductive -, resistive -, layers on insulating layers; After-treatment of these layers
- H01L21/47635—After-treatment of these layers
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- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1222—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer
- H01L27/1225—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer with semiconductor materials not belonging to the group IV of the periodic table, e.g. InGaZnO
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- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/41—Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions
- H01L29/417—Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions carrying the current to be rectified, amplified or switched
- H01L29/41725—Source or drain electrodes for field effect devices
- H01L29/41733—Source or drain electrodes for field effect devices for thin film transistors with insulated gate
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
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Abstract
本发明提供抑制了对IGZO的损伤的蚀刻液。本发明的蚀刻液的特征在于,其含有:羟基乙烷二膦酸(A)、膦酸(B)、过氧化氢(C)、硝酸(D)、氟化合物(E)、唑(F)及碱(G),前述膦酸(B)含有选自由二亚乙基三胺五亚甲基膦酸、N,N,N’,N’‑乙二胺四亚甲基膦酸及氨基三亚甲基膦酸组成的组中的1种以上,前述羟基乙烷二膦酸(A)的比例为0.01~0.1质量%的范围,前述膦酸(B)的比例为0.003~0.04质量%的范围。
Description
技术领域
本发明涉及半导体技术,特别是涉及IGZO的保护液及蚀刻液。
背景技术
作为氧化物半导体材料,铟·镓·锌氧化物(IGZO)作为有用的材料正在被研究。但是,已知有如下问题:IGZO由于容易被酸、碱蚀刻,因此使用这些蚀刻液形成源极/漏极布线时,作为基底的IGZO被腐蚀。
对了应对该问题,以往采用了在IGZO上形成保护层后形成源极/漏极布线的蚀刻阻挡(etch stop)型结构(参照图1),但是制造变烦杂,其结果,导致成本的增大。因此,为了采用不需要保护层的背沟道蚀刻(back channel etch)型结构(参照图2),期望抑制对IGZO的损伤、并可对各种布线材料蚀刻的蚀刻液(参照非专利文献1)。
另外,近年来如4K及8K面板所代表的那样,面板的高分辨率化正在迅速进展。若面板的高分辨率化进展,则用于驱动像素的布线图案变密,为了抑制由背光灯照射的光的损失,必须将布线宽度加工为较细。另一方面,为了确保流入至布线的电流量,需要高的形状的布线加工以增大布线截面积。即期望能够将布线的锥角加工为较高的蚀刻液。
目前,作为抑制对IGZO的损伤的蚀刻液,已知有日本特开2016-11342号公报(专利文献1)中记载的以低pH为特征的化学溶液,但不能达成充分的IGZO的防蚀性、加工性。
现有技术文献
专利文献
专利文献1:日本特开2016-11342号公报
非专利文献
非专利文献1:神户制钢技报Vol.65、No.2、Sep.2015、森田晋也等“BCE型TFT对应氧化物半导体材料”
发明内容
发明要解决的问题
这样的状况下,期望提供抑制对IGZO的损伤、并且可对布线材料进行蚀刻的蚀刻液。
用于解决问题的方案
本发明如下。
[1]蚀刻液,其含有:羟基乙烷二膦酸(A)、膦酸(B)、过氧化氢(C)、硝酸(D)、氟化合物(E)、唑(F)及碱(G),前述膦酸(B)含有选自由二亚乙基三胺五亚甲基膦酸、N,N,N’,N’-乙二胺四亚甲基膦酸及氨基三亚甲基膦酸组成的组中的1种以上,前述羟基乙烷二膦酸(A)的比例为0.01~0.1质量%的范围,前述膦酸(B)的比例为0.003~0.04质量%的范围。
[2]根据[1]所述的蚀刻液,其中,前述膦酸(B)为二亚乙基三胺五亚甲基膦酸。
[3]根据[1]或[2]所述的蚀刻液,其中,前述氟化合物(E)为氟化铵或酸性氟化铵。
发明的效果
根据本发明的优选方式,通过使用本发明的蚀刻液,能够防止IGZO免受酸及碱的腐蚀,不需要在IGZO上形成保护层,因此能够大幅降低制造成本。因此,可制作在蚀刻工序中防止IGZO腐蚀、并且具有高锥角的布线结构的良好的基板。特别是,在IGZO上具有包含铜层及钛层的多层薄膜的构成中,基于特别优选的蚀刻的加工成为可能。
附图说明
图1为在IGZO上设置有保护层的以往的蚀刻阻挡型结构的TFT示意图的一例。
图2为未设置保护层的背沟道蚀刻型结构的TFT示意图的一例。
图3为使用了本发明的蚀刻液时的布线截面的示意图的一例。
图4为使用了实施例或比较例的蚀刻液时的IGZO的截面观察的一例。
图5为使用了实施例或比较例的蚀刻液时的IGZO的表面观察的一例。
具体实施方式
本发明的蚀刻液通过含有羟基乙烷二膦酸(A)及特定的膦酸(B),从而能够具有对IGZO的防蚀性。另外,通过还含有过氧化氢(C)、硝酸(D)、氟化合物(E)、唑(F)及碱(G),从而能够得到具有对IGZO的防蚀性、并且可对布线材料蚀刻的组合物。
以下,对本发明的蚀刻液的各成分详细地进行说明。
[羟基乙烷二膦酸(HEDP)(A)]
羟基乙烷二膦酸(A)为式(1)所示的化合物。
HEDP(A)的蚀刻液中的比例为0.01~0.1质量%的范围,优选为0.03~0.08质量%的范围。通过使HEDP(A)的浓度范围处于该范围,从而能够赋予高的IGZO的防蚀性能,并且能够防止IGZO表面的粗糙。
[膦酸(B)]
通过与HEDP(A)一起使用膦酸(B),从而能够赋予高的IGZO的防蚀性、同时能够将布线形状加工成高的锥角。
本发明中的膦酸(B)为选自由二亚乙基三胺五亚甲基膦酸、N,N,N’,N’-乙二胺四亚甲基膦酸及氨基三亚甲基膦酸组成的组中的1种以上的膦酸。这些之中,N,N,N’,N’-乙二胺四亚甲基膦酸由于对IGZO的防蚀性高,因此优选。
膦酸(B)的蚀刻液中的比例为0.003~0.04质量%的范围,优选为0.01~0.03质量%的范围、更优选为0.015~0.03质量%的范围。通过使膦酸(B)的浓度范围处于该范围,从而能够达成高的IGZO的防蚀性能。
[过氧化氢(C)]
过氧化氢(C)具有作为氧化剂而将铜氧化的功能。
过氧化氢(C)的蚀刻液中的比例优选4.0~8.0质量%的范围、更优选为4.5~7.5质量%的范围、特别优选为5.0~6.5质量%的范围。通过使过氧化氢(C)的浓度范围处于该范围,从而能够适当地进行蚀刻速度的确保和布线的局部腐蚀的抑制。
[硝酸(D)]
硝酸(D)具有使被过氧化氢氧化的铜溶解的效果等。
硝酸(D)的蚀刻液中的比例优选0.8~7.0质量%的范围、更优选为1.5~6.5质量%的范围、特别优选为2.0~6.0质量%的范围。通过使硝酸(D)的浓度范围处于该范围,从而能够确保良好的蚀刻速率,并且能够得到良好的布线形状。
[氟化合物(E)]
氟化合物(E)具有对由钛系金属形成的阻挡层进行蚀刻的功能。
对于氟化合物(E)的种类,只要为产生氟离子的化合物,就没有限定。作为具体例,可列举出氢氟酸、氟化铵及酸性氟化铵,这些之中,氟化铵及酸性氟化铵由于为低毒性而优选。氟化合物(E)可以使用1种,也可以组合使用2种以上。
氟化合物(E)的蚀刻液中的比例优选0.2~0.8质量%的范围、更优选为0.2~0.6质量%、特别优选为0.2~0.5质量%的范围。通过使氟化合物(E)的浓度范围处于该范围,从而能够得到由钛系金属形成的阻挡层的良好的蚀刻速度。
[唑(F)]
唑(F)是为了进行基于pH的蚀刻速度的调整而使用的。作为唑(F)的具体例,可列举出1,2,4-三唑、1H-苯并三唑、5-甲基-1H-苯并三唑、3-氨基-1H-三唑等三唑类;1H-四唑、5-甲基-1H-四唑、5-苯基-1H-四唑、5-氨基-1H-四唑等四唑类;1,3-噻唑、4-甲基噻唑等噻唑类等。这些之中,优选四唑类,其中从在液体中与铜离子不形成不溶性的盐的方面来看,优选5-氨基-1H-四唑。唑(F)可以使用1种,也可以组合使用2种以上。
唑(F)在蚀刻液中的比例优选0.05~0.35质量%的范围、更优选为0.05~0.30质量%、特别优选为0.08~0.25质量%。通过使唑(F)的浓度范围处于该范围,从而能够适当地调整蚀刻速度,能够得到良好的布线形状。
[碱(G)]
碱(G)是为了进行基于pH的蚀刻速度的调整而使用的。碱(G)只要为通常作为蚀刻液而使用的种类,就没有限制,例如可列举出氨、氢氧化钾、氢氧化季铵及胺化合物。
作为胺化合物,可列举出乙胺、异丙基胺等烷基胺类;N-丙醇胺、N-甲基乙醇胺所代表的烷醇胺类;乙二胺所代表的二胺。这些之中,从不使过氧化氢的稳定性恶化的方面出发,优选氢氧化季铵、N-丙醇胺及N-丁基乙醇胺。碱(G)可以使用1种,也可以组合使用2种以上。
碱(G)的蚀刻液中的比例优选0.6~10质量%的范围,优选为1.0~9.0质量%、特别优选为2.0~8.0质量%的范围。通过使浓度范围处于该范围,从而能够适当地调节蚀刻速度。
[其他成分]
本发明的蚀刻液中可以在不损害本发明目的的范围内包含以往以来蚀刻液中使用的添加剂、过氧化氢稳定剂、表面活性剂、着色剂、消泡剂等。
[蚀刻液的制备方法]
本发明的蚀刻液通过在HEDP(A)、膦酸(B)、过氧化氢(C)、硝酸(D)、氟化合物(E)、唑(F)、碱(G)及根据需要的其他成分中添加水(优选超纯水)并进行搅拌直至变均匀为止来制备。
组成液的pH的范围没有特别限制,通常为1.5~2.8,优选为1.8~2.5。通过处于该范围,从而能够适当地防止对IGZO腐蚀、并且能够将布线材料蚀刻。
[蚀刻液的使用方法]
通过使本发明的蚀刻液与对象物接触,从而能够将对象物蚀刻。
使本发明的蚀刻液与对象物接触的方法没有特别限制,例如可以采用通过滴加(单片旋转处理)或喷雾等形式使其与对象物接触的方法、使对象物浸渍于本发明的蚀刻液中的方法。
使用本发明的蚀刻液的温度范围通常为10~70℃,优选为20~50℃。使用蚀刻液的时间通常为0.2~60分钟。作为蚀刻后的冲洗液,有机溶剂和水中的任意者均可以使用。
[半导体基板]
作为本发明的蚀刻液的对象的基板优选具有IGZO,IGZO只要为含有铟、镓、锌及氧而构成的半导体,就没有特别限制。上述氧化物可以为无定形结构,也可以具有结晶性。
使用IGZO作为例如薄膜晶体管(TFT:Thin Film Transistor)等电子元件的情况下,IGZO是使用溅射法等成膜工艺而在玻璃等基板上形成的。接着,将抗蚀剂等作为掩模并进行蚀刻,由此形成电极图案。进而在其上使用溅射法等成膜工艺形成铜(Cu)及钛(Ti)等,接着将抗蚀剂等作为掩模并进行蚀刻,由此形成源极/漏极电极。
图3为使用了本发明的蚀刻液时的布线截面的示意图的一例。对于图3所示那样的、在IGZO层(4)上,隔着含有钛的钛层等阻挡层(3)具备具有由含有铜的铜层形成的布线层(2)的多层薄膜的结构,优选用于平板显示器等显示装置等的布线,可特别有效地发挥本发明的蚀刻液的性能。根据本发明的优选方式,通过将抗蚀层(1)作为掩模并使用本发明的蚀刻液对该多层薄膜进行蚀刻,能够形成期望的布线结构。需要说明的是,在图3中,将从抗蚀层(1)端部到与抗蚀层(1)接触的布线层(2)端部为止的距离(a)的2倍称为顶部CD损失(a×2),将从抗蚀层(1)端部到与设置于布线(2)下的阻挡层(3)接触的布线层(2)端部为止的距离(b)的2倍称为底部CD损失(b×2)。另外,将从布线层(2)端部到阻挡层(3)的端部为止的距离(c)的2倍(c×2)称为拖尾(tailing)。另外,将布线层(2)端部的蚀刻面与下层的IGZO层(4)所成的角度称为锥角(5)。
实施例
以下,通过实施例更具体地对本发明进行说明,但可以在发挥本发明的效果的范围内适宜变更实施方式。
需要说明的是,只要没有特别指定,则%是指质量%。
[评价用基板]
<IGZO的蚀刻速率及表面状态评价用的基板(1)>
<对于包含铜层及钛层的多层薄膜的蚀刻性能评价用的基板(2)>
在玻璃基板上以厚度25nm溅射钛而形成钛层,接着以600nm的厚度溅射铜,层叠布线原材料的铜层。接着涂布抗蚀剂,将图案掩模曝光转印后,进行显影而形成布线图案,在玻璃基板上制作包含铜层及钛层的多层薄膜(100mm×100mm×1mm)。
[评价方法]
制备表1或2中记载的包含(C)、(D)、(E)、(F)及(G)成分浓度的组合物后,分别添加铜粉末6000ppm及钛粉末150ppm,搅拌至金属溶解为止。确认了金属的溶解后,以规定浓度添加(A)及(B)成分,作为蚀刻液。在各个蚀刻液中使基板(1)在35℃下静置浸渍20秒钟,由此进行蚀刻。其后进行水洗,使用氮气使其干燥。
利用n&k Analyzer 1280(n&k Technology Inc.)测定蚀刻后的膜厚,将其膜厚差除以蚀刻时间,由此算出蚀刻速率,按照以下的基准进行判定。
将E、G及P设为合格。
[IGZO表面状态]
将测定IGZO的蚀刻速率后的IGZO薄膜切断,使用扫描型电子显微镜(型号:S5000H型、株式会社日立制作所制)以倍率50000倍(加速电压2kV、加速电流10μA)对表面的粗糙程度进行观察,按照以下的基准进行判定。
E:平滑的表面状态
G:在表面产生略微的粗糙、用扫描型电子显微镜观察IGZO截面时,凹凸部的差小于25nm、或用扫描型电子显微镜观察IGZO表面时,平均单位面积(1200nm×1200nm)的空隙部分的产生数小于20处
B:在表面产生显著的粗糙、空隙,用扫描型电子显微镜观察IGZO截面时,凹凸部的差为25nm以上、或用扫描型电子显微镜观察IGZO表面时,平均单位面积(1200nm×1200nm)的空隙部分的产生数为20处以上
将E及G设为合格。
将IGZO的截面观察的一例示于图4,将表面观察的一例示于图5。
[对包含铜层及钛层的多层薄膜的蚀刻性能]
制备表1或2中记载的包含(C)、(D)、(E)、(F)及(G)成分浓度的组合物后,分别添加铜粉末6000ppm、钛粉末150ppm,搅拌至金属溶解为止。确认了金属的溶解后,以规定浓度添加(A)及(B)成分,作为蚀刻液。在各个蚀刻液中使基板(2)在35℃下静置150秒钟而进行蚀刻,其后进行水洗,使用氮气使其干燥。
将用上述蚀刻方法得到的包含铜层及钛层的多层薄膜试样切断,使用扫描型电子显微镜(型号:S5000H型、株式会社日立制作所制)以倍率50000倍(加速电压2kV、加速电流10μA)对截面进行观察。
基于得到的SEM图像,测定图3中所示的锥角5,按照以下的基准判定蚀刻后的形状。
锥角E:60°以上~小于70°
G:50以上~小于60°
B:小于50°或70°以上
将E及G设为合格。
将评价结果示于表1及2。
[表1]
[表2]
需要说明的是,表中的成分如下。
B1:N,N,N’,N’-乙二胺四亚甲基膦酸
B2:二亚乙基三胺五亚甲基膦酸
B3:氨基三亚甲基膦酸
B4:磷酸
B5:膦酸
B6:五亚乙基八亚甲基膦酸
E1:酸性氟化铵
F1:5-氨基-1H-四唑
G1:氢氧化季铵
G2:氢氧化钾
G3:N-丁基乙醇胺
G4:氨
G5:1-氨基-2-丙醇
附图标记说明
1.抗蚀层
2.布线层
3.阻挡层
4.IGZO层
5.锥角
a;顶部CD损失(a×2)
b;底部CD损失(b×2)
c;拖尾(c×2)
产业上的可利用性
本发明的蚀刻液可以适合用于包含IGZO的基板中的布线材料的蚀刻。
根据本发明的优选方式,可以防止腐蚀IGZO、并且能制成具有高锥角的布线结构的基板。
Claims (19)
1.一种蚀刻液,其含有:羟基乙烷二膦酸(A)、膦酸(B)、过氧化氢(C)、硝酸(D)、氟化合物(E)、唑(F)及碱(G),所述膦酸(B)含有选自由二亚乙基三胺五亚甲基膦酸、N,N,N’,N’-乙二胺四亚甲基膦酸及氨基三亚甲基膦酸组成的组中的1种以上,所述羟基乙烷二膦酸(A)的比例为0.01~0.1质量%的范围,所述膦酸(B)的比例为0.003~0.04质量%的范围。
2.根据权利要求1所述的蚀刻液,其中,所述膦酸(B)为选自由二亚乙基三胺五亚甲基膦酸及N,N,N’,N’-乙二胺四亚甲基膦酸组成的组中的1种以上。
3.根据权利要求1或2所述的蚀刻液,其中,所述膦酸(B)为二亚乙基三胺五亚甲基膦酸。
4.根据权利要求1或2所述的蚀刻液,其中,所述膦酸(B)在蚀刻液中的比例为0.01~0.03质量%的范围。
5.根据权利要求1或2所述的蚀刻液,其中,所述氟化合物(E)为氟化铵或酸性氟化铵。
6.根据权利要求1或2所述的蚀刻液,其中,所述氟化合物(E)在蚀刻液中的比例为0.2~0.8质量%的范围。
7.根据权利要求1或2所述的蚀刻液,其中,所述过氧化氢(C)在蚀刻液中的比例为4.0~8.0质量%的范围。
8.根据权利要求1或2所述的蚀刻液,其中,所述硝酸(D)在蚀刻液中的比例为0.8~7.0质量%的范围。
9.根据权利要求1或2所述的蚀刻液,其中,所述唑(F)为5-氨基-1H-四唑。
10.根据权利要求1或2所述的蚀刻液,其中,所述唑(F)在蚀刻液中的比例为0.05~0.35质量%的范围。
11.根据权利要求1或2所述的蚀刻液,其中,所述碱(G)为选自由氨、氢氧化钾、氢氧化季铵及胺化合物组成的组中的1种以上。
12.根据权利要求1或2所述的蚀刻液,其中,所述碱(G)为选自由氨、氢氧化季铵、氢氧化钾、N-丁基乙醇胺及1-氨基-2-丙醇组成的组中的1种以上。
13.根据权利要求1或2所述的蚀刻液,其中,所述碱(G)在蚀刻液中的比例为0.6~10质量%的范围。
15.一种蚀刻方法,其中,使含有铟·镓·锌氧化物(IGZO)的基板与权利要求1~14中任一项所述的蚀刻液接触,所述铟·镓·锌氧化物(IGZO)含有铟、镓、锌及氧。
16.一种蚀刻方法,其中,使含有铟·镓·锌氧化物(IGZO)和在铟·镓·锌氧化物(IGZO)上形成的布线材料的基板与权利要求1~14中任一项所述的蚀刻液接触,由此对在铟·镓·锌氧化物(IGZO)上形成的布线材料进行蚀刻,所述铟·镓·锌氧化物(IGZO)含有铟、镓、锌及氧。
17.一种蚀刻方法,其中,使含有铟·镓·锌氧化物(IGZO)和在铟·镓·锌氧化物(IGZO)上形成的布线层及阻挡层的基板与权利要求1~14中任一项所述的蚀刻液接触,由此对在铟·镓·锌氧化物(IGZO)上形成的阻挡层进行蚀刻,所述铟·镓·锌氧化物(IGZO)含有铟、镓、锌及氧。
18.一种显示装置的制造方法,其具有如下工序:使含有铟·镓·锌氧化物(IGZO)和在铟·镓·锌氧化物(IGZO)上形成的布线材料的基板与权利要求1~14中任一项所述的蚀刻液接触,由此对在铟·镓·锌氧化物上形成的布线材料进行蚀刻,所述铟·镓·锌氧化物(IGZO)含有铟、镓、锌及氧。
19.一种显示装置的制造方法,其具有如下工序:使含有铟·镓·锌氧化物(IGZO)和在铟·镓·锌氧化物(IGZO)上形成的布线层及阻挡层的基板与权利要求1~14中任一项所述的蚀刻液接触,由此对在铟·镓·锌氧化物上形成的阻挡层进行蚀刻,所述铟·镓·锌氧化物(IGZO)含有铟、镓、锌及氧。
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