JP2005163108A - Etching agent, and etching method using the same - Google Patents
Etching agent, and etching method using the same Download PDFInfo
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- JP2005163108A JP2005163108A JP2003403548A JP2003403548A JP2005163108A JP 2005163108 A JP2005163108 A JP 2005163108A JP 2003403548 A JP2003403548 A JP 2003403548A JP 2003403548 A JP2003403548 A JP 2003403548A JP 2005163108 A JP2005163108 A JP 2005163108A
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- hydrogen peroxide
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- alkali metal
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- 238000005530 etching Methods 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 239000003518 caustics Substances 0.000 claims abstract description 9
- 230000002378 acidificating effect Effects 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000010409 thin film Substances 0.000 abstract description 16
- 230000003449 preventive effect Effects 0.000 abstract description 13
- 238000002845 discoloration Methods 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 150000003536 tetrazoles Chemical class 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- USYCQABRSUEURP-UHFFFAOYSA-N 1h-benzo[f]benzimidazole Chemical compound C1=CC=C2C=C(NC=N3)C3=CC2=C1 USYCQABRSUEURP-UHFFFAOYSA-N 0.000 description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- -1 alkali metal acetate Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- NNRAOBUKHNZQFX-UHFFFAOYSA-N 2H-benzotriazole-4-thiol Chemical compound SC1=CC=CC2=C1NN=N2 NNRAOBUKHNZQFX-UHFFFAOYSA-N 0.000 description 1
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical class NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 description 1
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical compound SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 description 1
- RKMOGOGTQIHYMN-UHFFFAOYSA-N 4-(2-methylphenyl)-2h-benzotriazole Chemical compound CC1=CC=CC=C1C1=CC=CC2=NNN=C12 RKMOGOGTQIHYMN-UHFFFAOYSA-N 0.000 description 1
- GCWGMSSRPLWOCZ-UHFFFAOYSA-N 4-butoxy-2h-benzotriazole Chemical compound CCCCOC1=CC=CC2=NNN=C12 GCWGMSSRPLWOCZ-UHFFFAOYSA-N 0.000 description 1
- IVNKBULLSPPOOW-UHFFFAOYSA-N 4-hexoxy-2h-benzotriazole Chemical compound CCCCCCOC1=CC=CC2=NNN=C12 IVNKBULLSPPOOW-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- MAAJEDCWIWCFDB-UHFFFAOYSA-N 4-pentoxy-2h-benzotriazole Chemical compound CCCCCOC1=CC=CC2=C1NN=N2 MAAJEDCWIWCFDB-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
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- INBDCPLKPRJASK-UHFFFAOYSA-N CO[SiH2]CCCC=1NC=CN1 Chemical compound CO[SiH2]CCCC=1NC=CN1 INBDCPLKPRJASK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000008351 acetate buffer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- KDNFLUWYIMPBSA-UHFFFAOYSA-N hydrogen peroxide;1,3,5-triazine-2,4,6-triamine Chemical compound OO.NC1=NC(N)=NC(N)=N1 KDNFLUWYIMPBSA-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
Abstract
Description
本発明は、エッチング剤及びこれを用いたエッチング方法に関し、特に、Ｔｉ及び／又はＷを含有する薄膜のエッチングに適したエッチング剤及びこれを用いたエッチング方法に関する。 The present invention relates to an etching agent and an etching method using the same, and more particularly to an etching agent suitable for etching a thin film containing Ti and / or W and an etching method using the same.
近年、ＷＬ−ＣＳＰ（ウェハレベルチップサイズドパッケージ）技術等において、シリコンウエハに配線を形成するなど、近年電子デバイスの製造に当たって、配線や電極材料としてＣｕが使用されている。
このようなＣｕに対するバリア膜としては、Ｔｉ、Ｗ、ＴｉＷ、ＴｉＮ、ＷＣｏ等のＴｉ及び／又はＷを含有する薄膜等が使用されているので、その製造工程には、それら薄膜をエッチングする工程が存在する。従来は、過酸化水素を用いて、それら薄膜をエッチングする方法が一般的に用いられてきた（特許文献１及び２参照）。
しかしながら、過酸化水素のみによるエッチングにおいては、そのエッチング時間が著しく長く、かつＣｕ配線表面の酸化による変色のため、次工程において酸洗浄を行い、表面酸化膜を除去する必要があった。また、回路中の抵抗の一部として用いられる無電解Ｎｉメッキ部も同様に変色をしてしまう。
In recent years, Cu has been used as a wiring or electrode material in the manufacture of electronic devices in recent years, such as the formation of wiring on silicon wafers in WL-CSP (wafer level chip sized package) technology and the like.
As such a barrier film against Cu, a thin film containing Ti and / or W such as Ti, W, TiW, TiN, WCo or the like is used. Therefore, in the manufacturing process, the thin film is etched. Exists. Conventionally, a method of etching these thin films using hydrogen peroxide has been generally used (see Patent Documents 1 and 2).
However, in the etching using only hydrogen peroxide, the etching time is remarkably long, and due to the discoloration due to oxidation of the Cu wiring surface, it is necessary to perform acid cleaning in the next step to remove the surface oxide film. In addition, the electroless Ni plating portion used as a part of the resistance in the circuit is also discolored.
一方、装飾品のＴｉＮ被膜の除去には、過酸化水素及びアルカリが用いられている（特許文献３参照）。過酸化水素とアルカリの混合液を電子デバイスの製造に用いると、異種金属間に生ずる局部電池効果によりＣｕパターン下に著しいアンダーカットを生じ、バリア膜としての本来の機能を低下させる。また、過度のアンダーカットが生じた場合には、パターンの剥離・脱落が発生してしまう。 On the other hand, hydrogen peroxide and alkali are used to remove the TiN film of the decorative article (see Patent Document 3). When a mixed solution of hydrogen peroxide and alkali is used for manufacturing an electronic device, a significant undercut occurs under the Cu pattern due to a local battery effect generated between different metals, and the original function as a barrier film is lowered. In addition, when excessive undercutting occurs, pattern peeling / dropping occurs.
従って本発明の目的は、(i)Ｃｕパターン表面や無電解Ｎｉメッキ部に酸化・変色させない、(ii)Ｃｕパターン下のアンダーカットを極力抑制する、(iii)Ｔｉ及び／又はＷを含有する薄膜を短時間で選択的にエッチングすることのできるエッチング剤及びこれを用いたエッチング方法を提供することにある。 Accordingly, the object of the present invention is to (i) prevent oxidation or discoloration of the Cu pattern surface or electroless Ni plating portion, (ii) suppress undercut under the Cu pattern as much as possible, and (iii) contain Ti and / or W. An object of the present invention is to provide an etching agent capable of selectively etching a thin film in a short time and an etching method using the same.
本発明者らは上記に鑑み鋭意研究の結果、本発明に到達した。
即ち本発明のエッチング剤は、ｐＨが３．０以上７．０以下の酸性域の水溶液であって、過酸化水素、アルカリ金属イオン及び防錆剤を含有することを特徴とする。
また、本発明のエッチング剤は、ｐＨが７．０を超え８．０以下のアルカリ性域の水溶液であって、過酸化水素及び苛性アルカリを供給源とするアルカリ金属イオンを含有することを特徴とする。
さらに、前記エッチング剤を用いて、Ｔｉ及び／又はＷを含有する材料をエッチング対象としてエッチングすることを特徴とするエッチング方法である。
加えて、前記エッチング対象には、Ｃｕ又はＮｉを少なくとも含有する被保護材料が配置されていることを特徴とするエッチング方法である。
The present inventors have reached the present invention as a result of intensive studies in view of the above.
That is, the etching agent of the present invention is an aqueous solution in an acidic region having a pH of 3.0 or more and 7.0 or less, and is characterized by containing hydrogen peroxide, alkali metal ions, and a rust inhibitor.
The etching agent of the present invention is an aqueous solution in an alkaline region having a pH of more than 7.0 and not more than 8.0, characterized by containing alkali metal ions having hydrogen peroxide and caustic as a supply source. To do.
Furthermore, the etching method is characterized in that the material containing Ti and / or W is etched using the etching agent as an etching target.
In addition, in the etching method, the object to be etched is provided with a protected material containing at least Cu or Ni.
本発明の効果は、(i)Ｃｕパターン表面や無電解Ｎｉメッキ部に酸化・変色させない、(ii)Ｃｕパターン下のアンダーカットを極力抑制する、(iii)Ｔｉ及び／又はＷを含有する薄膜を短時間で選択的にエッチングすることのできるエッチング剤及びこれを用いたエッチング方法を提供したことにある。 The effects of the present invention are as follows: (i) the surface of the Cu pattern and electroless Ni-plated portion are not oxidized or discolored; (ii) the undercut under the Cu pattern is suppressed as much as possible; (iii) a thin film containing Ti and / or W The present invention provides an etching agent that can be selectively etched in a short time and an etching method using the same.
本発明の一方のエッチング剤は、ｐＨが３．０以上７．０以下の酸性域の水溶液であって、過酸化水素、アルカリ金属イオン及び防錆剤を含有することを特徴とするエッチング剤である。
この酸性域のエッチング剤は、３．０以上７．０以下のｐＨとすると共にアルカリ金属イオン及び防錆剤を含有するので、アンダーカットを抑制すると共に効率よくエッチングし、酸性域であってもＣｕの表面や無電解Ｎｉメッキ部の酸化・変色を抑制することができる。
One etching agent of the present invention is an aqueous solution in an acidic region having a pH of 3.0 or more and 7.0 or less, which contains hydrogen peroxide, alkali metal ions, and a rust preventive agent. is there.
The etching agent in the acidic region has a pH of 3.0 or more and 7.0 or less and contains an alkali metal ion and a rust preventive agent. Therefore, the etching is efficiently performed while suppressing undercutting. Oxidation and discoloration of the Cu surface and electroless Ni plating can be suppressed.
本発明の酸性域のエッチング剤に係る過酸化水素の濃度は、０．５〜５０質量％が好ましく、１〜４０質量％が特に好ましい。０．５質量％未満であると、Ｔｉ及び／又はＷを含有する材料薄膜を効率的に除去することができなくなり、５０質量％を超えると工業化適正が低くなるので好ましくない。 The concentration of hydrogen peroxide related to the etching agent in the acidic region of the present invention is preferably 0.5 to 50% by mass, particularly preferably 1 to 40% by mass. If it is less than 0.5% by mass, the material thin film containing Ti and / or W cannot be efficiently removed, and if it exceeds 50% by mass, the industrialization suitability is lowered, which is not preferable.
本発明の酸性域のエッチング剤中に過酸化水素を含有させる方法は、特に限定されることはない。例えば、過酸化水素水或いは平衡過酢酸などの過酸化水素含有物をベースとして用いたり、本発明を構成する他の成分のベースに過酸化水素（水）或いは平衡過酢酸などの過酸化水素含有物を投入してもよく、また、ナトリウム塩、カリウム塩、アンモニウム塩などの過炭酸塩、ナトリウム塩、カリウム塩、アンモニウム塩などの過ホウ酸塩、メラミン過酸化水素付加物などの過酸化水素放出性原料を同様に投入してもよい。 The method for incorporating hydrogen peroxide into the acidic etching agent of the present invention is not particularly limited. For example, hydrogen peroxide containing materials such as hydrogen peroxide water or equilibrium peracetic acid are used as a base, or hydrogen peroxide (water) or hydrogen peroxide containing equilibrium peracetic acid is used as the base of other components constituting the present invention. In addition, percarbonate such as sodium salt, potassium salt and ammonium salt, perborate such as sodium salt, potassium salt and ammonium salt, hydrogen peroxide such as melamine hydrogen peroxide adduct A releasable raw material may be similarly charged.
本発明の酸性域のエッチング剤に係るアルカリ金属イオンは、特に限定されることはない。例えばＬｉイオン、Ｎａイオン、Ｋイオン等が挙げられるが、工業化適正の観点からＮａイオン及び／又はＫイオンが好ましく、Ｎａイオンが特に好ましい。
これらのアルカリ金属イオンの供給源としては、苛性アルカリ、アルカリ金属リン酸塩、アルカリ金属硫酸塩、アルカリ金属硝酸塩及びアルカリ金属酢酸塩等が挙げられる。
The alkali metal ion related to the etching agent in the acidic region of the present invention is not particularly limited. For example, Li ion, Na ion, K ion and the like can be mentioned. From the viewpoint of industrialization suitability, Na ion and / or K ion is preferable, and Na ion is particularly preferable.
Examples of the supply source of these alkali metal ions include caustic alkali, alkali metal phosphate, alkali metal sulfate, alkali metal nitrate, and alkali metal acetate.
本発明の酸性域のエッチング剤に係るアルカリ金属イオンの濃度は、エッチング効率を上昇させる観点から、比較的多めのアルカリ金属イオン濃度となる。その濃度は、４〜１００ｍｍｏｌ／Ｌが好ましく、１０〜７０ｍｍｏｌ／Ｌが特に好ましい。４ｍｍｏｌ／Ｌ未満であるとエッチング効率が十分ではなく、１００ｍｍｏｌ／Ｌを超えるとアンダーカットが増大するので好ましくない。 The concentration of alkali metal ions related to the etching agent in the acidic region of the present invention is a relatively large concentration of alkali metal ions from the viewpoint of increasing the etching efficiency. The concentration is preferably 4 to 100 mmol / L, particularly preferably 10 to 70 mmol / L. If it is less than 4 mmol / L, the etching efficiency is not sufficient, and if it exceeds 100 mmol / L, the undercut increases, which is not preferable.
本発明の酸性域のエッチング剤は、防錆剤を含有する。防錆剤は、ｐＨ３．０以上の酸性域において、エッチングの観点から多量のアルカリ金属イオンが存在していてもＣｕの表面や無電解Ｎｉメッキ部が酸化・変色してしまうのを抑制する効果がある。
本発明の酸性域のエッチング剤に係る防錆剤は、Ｃｕに対して有効な防錆効果を有する防錆剤である。例えばアゾール化合物系防錆剤があげられ、１，２，３−トリアゾール、１，２，４−トリアゾール、３−アミノ−１，２，４−トリアゾール等のアミノトリアゾール、トリルトリアゾール等のトリアゾール系防錆剤、ベンゾトリアゾール、５−メチル・１Ｈ−ベンゾトリアゾール、４−メチル・１Ｈ−ベンゾトリアゾール、５，６−ジメチル・１Ｈ−ベンゾトリアゾール等のアルキルベンゾトリアゾール、ブチルオキシベンゾトリアゾール、ペンチルオキシベンゾトリアゾール、ヘキシルオキシベンゾトリアゾール等のアルコキシベンゾトリアゾール、トリルベンゾトリアゾール、メルカプトベンゾトリアゾール等のベンゾトリアゾール系防錆剤、テトラゾール、５−アミノテトラゾール等のアミノテトラゾール、５−フェニル−１，２，３，４−テトラゾール、１−フェニル−５−メルカプト−テトラゾール等のテトラゾール系防錆剤、イミダゾール、アルキルイミダゾール、２−フェニル−イミダゾール、２−フェニル−４−メチル−イミダゾール、ポリビニル−イミダゾール、Ｎ−トリメトキシシリルプロピル−イミダゾール、イミダソール環含有ジアミノ−ｓ−トリアジン等のイミダゾール系防錆剤、ベンゾイミダゾール、２−メルカプト−ベンゾイミダゾール等のベンゾイミダゾール系防錆剤、ナフトイミダゾール等のナフトイミダゾール系防錆剤、チアゾール、２−メルカプト−チアゾール等のチアゾール系防錆剤、ベンゾチアゾール、２−メルカプト−ベンゾチアゾール等のベンゾチアゾール系防錆剤、及び同様の構造を持つチオカルバミン酸誘導体系防錆剤等を例示することができるが、本発明の効果をより顕著に得る観点からベンゾトリアゾール系防錆剤及びテトラゾール系防錆剤が好ましい。
The acidic range etching agent of the present invention contains a rust inhibitor. The rust preventive has an effect of suppressing oxidation and discoloration of the Cu surface and the electroless Ni-plated portion even in the presence of a large amount of alkali metal ions from the viewpoint of etching in an acidic range of pH 3.0 or higher. There is.
The rust inhibitor related to the etching agent in the acidic region of the present invention is a rust inhibitor having an effective rust preventive effect on Cu. Examples include azole compound rust preventives, aminotriazoles such as 1,2,3-triazole, 1,2,4-triazole and 3-amino-1,2,4-triazole, and triazole type anti-corrosion such as tolyltriazole. Rust agent, benzotriazole, 5-methyl · 1H-benzotriazole, 4-methyl · 1H-benzotriazole, alkylbenzotriazole such as 5,6-dimethyl · 1H-benzotriazole, butyloxybenzotriazole, pentyloxybenzotriazole, Alkoxybenzotriazole such as hexyloxybenzotriazole, benzotriazole rust preventive such as tolylbenzotriazole and mercaptobenzotriazole, aminotetrazole such as tetrazole and 5-aminotetrazole, 5-phenyl-1,2, , 4-tetrazole, 1-phenyl-5-mercapto-tetrazole and other tetrazole rust inhibitors, imidazole, alkylimidazole, 2-phenyl-imidazole, 2-phenyl-4-methyl-imidazole, polyvinyl-imidazole, N-tri Imidazole rust preventives such as methoxysilylpropyl-imidazole and imidasol ring-containing diamino-s-triazine, benzimidazole rust preventives such as benzimidazole and 2-mercapto-benzimidazole, and naphthimidazole rust preventives such as naphthimidazole , Thiazole, 2-mercapto-thiazole and other thiazole rust preventives, benzothiazole, 2-mercapto-benzothiazole and other benzothiazole rust preventives, and thiocarbamic acid derivative rust preventives having the same structure Can Shimesuru, from the viewpoint of obtaining the effects of the present invention more remarkably benzotriazole corrosion inhibitor and tetrazole anticorrosive agent.
本発明の酸性域のエッチング剤に係る防錆剤の濃度は、０．０５〜１質量％が好ましく、０．１〜０．８質量％が特に好ましい。０．０５質量％未満であるとＣｕの表面や無電解Ｎｉメッキ部が変色してしまい、１質量％を超えるとエッチング効率の低下やアンダーカットの増大を招いてしまうので好ましくない。 The concentration of the rust inhibitor according to the etching agent in the acidic region of the present invention is preferably 0.05 to 1% by mass, particularly preferably 0.1 to 0.8% by mass. If it is less than 0.05% by mass, the surface of Cu or the electroless Ni-plated portion is discolored, and if it exceeds 1% by mass, etching efficiency is decreased and undercut is increased, which is not preferable.
次に、本発明の他方のエッチング剤は、ｐＨが７．０を超え８．０以下のアルカリ性域の水溶液であり、過酸化水素及び苛性アルカリを供給源とするアルカリ金属イオンを含有することを特徴とする。
このアルカリ性域のエッチング剤は、７．０を超え８．０以下のｐＨであるので、Ｃｕの表面や無電解Ｎｉメッキ部が酸化・変色することはない。さらに、苛性アルカリを供給源とするアルカリ金属イオンを所定量で含有するのでｐＨ８．０以下のアルカリ性域であっても、アンダーカットを極力抑制し、且つエッチング効率を上昇させることができる。
Next, the other etching agent of the present invention is an alkaline aqueous solution having a pH of more than 7.0 and not more than 8.0, and contains alkali metal ions having hydrogen peroxide and caustic alkali as sources. Features.
Since the alkaline etching agent has a pH of more than 7.0 and not more than 8.0, the surface of Cu and the electroless Ni-plated portion are not oxidized or discolored. Furthermore, since a predetermined amount of alkali metal ions containing caustic as a supply source is contained, undercut can be suppressed as much as possible and etching efficiency can be increased even in an alkaline region having a pH of 8.0 or less.
本発明のアルカリ性域のエッチング剤に係る過酸化水素の濃度及びその含有方法は、前記酸性域のエッチング剤の場合と同様である。 The concentration of hydrogen peroxide and the method of containing the hydrogen peroxide related to the alkaline etching agent of the present invention are the same as in the acidic etching agent.
本発明のアルカリ性域のエッチング剤に係るアルカリ金属イオンは、エッチング効率に優れた苛性アルカリを供給源とするものであり、ＮａＯＨ、ＫＯＨ、ＬｉＯＨ等が挙げられるが、工業化適正の観点からＮａＯＨ、ＫＯＨが好ましく、ＮａＯＨが特に好ましい。
このような苛性アルカリを供給源とするアルカリ金属イオンは、Ｌｉイオン、Ｎａイオン、Ｋイオン等が挙げられるが、工業化適正の観点からＮａイオン及び／又はＫイオンが好ましく、Ｎａイオンが特に好ましい。
The alkali metal ions related to the etching agent in the alkaline region of the present invention are those having caustic alkali excellent in etching efficiency as the supply source, and examples thereof include NaOH, KOH, LiOH, etc. From the viewpoint of industrialization appropriateness, NaOH, KOH And NaOH is particularly preferred.
Examples of such alkali metal ions using caustic as a supply source include Li ions, Na ions, K ions, and the like, but Na ions and / or K ions are preferable from the viewpoint of industrialization suitability, and Na ions are particularly preferable.
本発明のアルカリ性域のエッチング剤に係るアルカリ金属イオンの含有濃度は、４〜４５ｍｍｏｌ／Ｌが好ましく、１０〜３０ｍｍｏｌ／Ｌが特に好ましい。４ｍｍｏｌ／Ｌ未満であるとエッチング効率が十分ではなく、４５ｍｍｏｌ／Ｌを超えるとアンダーカットが増大するので好ましくない。 The content of alkali metal ions related to the etching agent in the alkaline region of the present invention is preferably 4 to 45 mmol / L, particularly preferably 10 to 30 mmol / L. If it is less than 4 mmol / L, the etching efficiency is not sufficient, and if it exceeds 45 mmol / L, the undercut increases, which is not preferable.
本発明の酸性域及びアルカリ性域のエッチング剤において、ｐＨを上記の範囲に維持する方法は特に限定されるものではなく、酸、塩基など公知のｐＨ調整剤を用いて調整すればよい。但し、塩化物イオンを含有するものはエッチング効率を低下させる可能性があるので他の物を使用することが好ましい。なお、エッチングの進行に伴ってｐＨが変動することがあるので、変動が上記のｐＨ範囲を外れるような場合は、例えば弱酸及び弱酸と強塩基の塩など公知のｐＨ緩衝剤を用いることが好ましい。また、ｐＨ検知手段とｐＨ調整剤供給手段を備えたエッチング槽を用いるなどして随時ｐＨを調整することも好ましい。
本発明に使用可能なｐＨ緩衝剤は、例えば酢酸塩系緩衝剤、リン酸塩系緩衝剤が挙げられ、酢酸ナトリウム、酢酸カリウム、リン酸二水素カリウム、リン酸二水素ナトリウム等いずれも使用することができるが、本発明の効果をより顕著に得る観点からリン酸二水素カリウムが好ましい。
In the acidic range and alkaline range etching agents of the present invention, the method for maintaining the pH in the above range is not particularly limited, and may be adjusted using a known pH adjuster such as an acid or a base. However, those containing chloride ions may reduce etching efficiency, so it is preferable to use other materials. In addition, since the pH may fluctuate with the progress of etching, when the fluctuation is out of the above pH range, it is preferable to use a known pH buffer such as a weak acid and a salt of a weak acid and a strong base. . It is also preferable to adjust the pH as needed by using an etching tank equipped with a pH detection means and a pH adjuster supply means.
Examples of the pH buffer that can be used in the present invention include an acetate buffer and a phosphate buffer, and any of sodium acetate, potassium acetate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, etc. is used. However, potassium dihydrogen phosphate is preferable from the viewpoint of obtaining the effects of the present invention more remarkably.
本発明のエッチング剤は、本発明の効果を阻害しない範囲内で所望により任意の添加剤を使用することができる。例えば過酸化水素安定剤を配合することができ、従来より過酸化水素安定剤として公知であるＥＤＴＡ、ＤＴＰＡ、ＮＴＡ等のキレート剤若しくは金属封鎖剤等の添加剤を使用することができる。これらの使用によりエッチング剤の効果を安定的に持続させることが可能である。 In the etching agent of the present invention, any additive can be used as desired within a range not impairing the effects of the present invention. For example, a hydrogen peroxide stabilizer can be blended, and an additive such as a chelating agent such as EDTA, DTPA, NTA or a metal sequestering agent that has been conventionally known as a hydrogen peroxide stabilizer can be used. By using these, it is possible to stably maintain the effect of the etching agent.
また、本発明は、酸性域及びアルカリ性域のエッチング剤を用いてＴｉ及び／又はＷを含有するエッチング対象をエッチングする方法である。
エッチング対象には、Ｔｉ及び／又はＷを含有する材料、例えばＴｉ、Ｗ、ＴｉＷ、ＴｉＮ、ＷＣｏ及びこれらが更に他の金属もしくは非金属元素（例えば、Ｃｒ、Ａｌ、Ｂ、Ｏ、Ｎ等）を含有する材料等を挙げることができる。
Moreover, this invention is a method of etching the etching object containing Ti and / or W using the etching agent of an acidic region and an alkaline region.
Etching objects include materials containing Ti and / or W, such as Ti, W, TiW, TiN, WCo, and other metal or non-metal elements (for example, Cr, Al, B, O, N, etc.) The material etc. which contain can be mentioned.
また、前記エッチング対象には、Ｃｕ又はＮｉを少なくとも含有する被保護材料が配置されていてもよい。
被保護材料は、例えばＣｕ、Ｎｉ或いはこれらが更に他の金属及び／又は非金属元素（エッチング対象と同一でない）を含有する材料等を挙げることができる。
本発明のエッチング剤は、エッチング対象を効率的に除去する反面、エッチング対象と同時に配置されている被保護材料をエッチングしないか、若しくは実質的にエッチングしないと言える程度にわずかにしかエッチングしない。
例えば、シリコンウエハ上にＣｕ配線やＣｕ電極、或いは無電解Ｎｉメッキによる抵抗部材などが配置されたＬＳＩなどの電子デバイスの製造において、これらの電子デバイスに配置されているＴｉ及び／又はＷを含有する材料からなるバリアメタル層の薄膜を除去するのに適している。即ち、本発明のエッチング剤は、Ｃｕパターン表面や無電解Ｎｉメッキ部に酸化・変色等の悪影響を与えず、且つＣｕパターン下のアンダーカットを極力抑制し、Ｔｉ及び／又はＷを含有する材料薄膜を短時間で選択的にエッチングすることができる。
Moreover, the to-be-etched object may be provided with a protected material containing at least Cu or Ni.
Examples of the material to be protected include Cu, Ni, or a material in which these further contain other metals and / or non-metallic elements (not the same as the etching target).
While the etching agent of the present invention efficiently removes the object to be etched, the material to be protected disposed at the same time as the object to be etched is not etched or etched only slightly to the extent that it cannot be substantially etched.
For example, in the manufacture of electronic devices such as LSIs in which Cu wiring, Cu electrodes, or resistance members made of electroless Ni plating are arranged on a silicon wafer, Ti and / or W arranged in these electronic devices are contained. It is suitable for removing the thin film of the barrier metal layer made of the material to be used. That is, the etching agent of the present invention does not give adverse effects such as oxidation and discoloration to the Cu pattern surface and the electroless Ni plating portion, and suppresses undercut under the Cu pattern as much as possible, and contains Ti and / or W. The thin film can be selectively etched in a short time.
エッチング条件は特に限定されるものではなく、エッチング対象の形状や膜厚などに応じて任意に設定することができる。
例えば、エッチング温度は、１０℃〜５０℃が好ましく、２０℃〜４０℃が特に好ましい。１０℃未満であるとエッチング速度が遅く工業的な効率を低下させることがあり、５０℃を超えるとアンダーカットを増大させることがあるので好ましくない。なお、エッチング剤の温度は反応熱により上昇することがあるので、必要なら上記温度範囲内に維持するよう公知の手段によって温度制御してもよい。
また、エッチング時間は、エッチング対象が完全にエッチングされるに十分必要な時間とすればよいので特に限定されるものではない。例えば、半導体装置のバリア膜などにおけるような膜厚１００〜５００ｎｍ程度のエッチング対象であれば、上記温度範囲であれば２分〜１０分程度エッチングを行えばよい。なお、アンダーカット抑制の観点から、エッチング完了後は速やかに処理を終了することが好ましい。
さらに、エッチング方式も特に限定されるものではなく、浸漬法でもスプレー法でもよく、公知のエッチング方式によってエッチングすればよい。
以下に実施例を挙げ、本発明をさらに説明するが、本発明はこれらに限定されるもので
はない。
The etching conditions are not particularly limited, and can be arbitrarily set according to the shape and film thickness of the etching target.
For example, the etching temperature is preferably 10 ° C to 50 ° C, particularly preferably 20 ° C to 40 ° C. If it is less than 10 ° C., the etching rate may be slow and industrial efficiency may be lowered, and if it exceeds 50 ° C., the undercut may be increased. Since the temperature of the etching agent may be increased by reaction heat, the temperature may be controlled by a known means so as to maintain it within the above temperature range if necessary.
Further, the etching time is not particularly limited because it may be a time sufficient for the object to be etched to be completely etched. For example, in the case of an etching target having a thickness of about 100 to 500 nm as in a barrier film of a semiconductor device, the etching may be performed for about 2 to 10 minutes within the above temperature range. Note that, from the viewpoint of suppressing undercutting, it is preferable to terminate the processing promptly after completion of etching.
Further, the etching method is not particularly limited, and an immersion method or a spray method may be used, and etching may be performed by a known etching method.
EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.
〔実施例１〜１１及び比較例１〜２〕
厚さ０．５ｍｍの６インチシリコンウエハ上に１５０ｎｍのＴｉ−Ｗ薄膜（Ｔｉ：Ｗ重量比１：９）をスパッタにて形成し、その上に厚さ１０μｍのＣｕパターン（Ｌ／Ｓ ５０μｍ）を形成しサンプルとした。表１に示した組成の各エッチング剤（１Ｌ：３０℃）中に浸漬してパターン部分以外のＴｉ−Ｗ薄膜をエッチングした。
[Examples 1-11 and Comparative Examples 1-2]
A 150 nm Ti—W thin film (Ti: W weight ratio 1: 9) is formed on a 0.5 mm thick 6-inch silicon wafer by sputtering, and a 10 μm thick Cu pattern (L / S 50 μm) is formed thereon. To form a sample. The Ti—W thin film other than the pattern portion was etched by dipping in each etching agent (1 L: 30 ° C.) having the composition shown in Table 1.
表面のＴｉ−Ｗ薄膜のエッチングは、その部位の絶縁抵抗を測定することにより確認し、Ｔｉ−Ｗ薄膜が完全にエッチングできるまでの時間を測定、エッチング速度を算出した。また、同時にＣｕパターン表面の酸化・変色について目視及びマイクロスコープにて観察した。 Etching of the Ti—W thin film on the surface was confirmed by measuring the insulation resistance at that site, and the time until the Ti—W thin film could be completely etched was measured to calculate the etching rate. Simultaneously, oxidation and discoloration of the Cu pattern surface were observed visually and with a microscope.
アンダーカットの測定は、Ｔｉ−Ｗ薄膜エッチング後のウエハについて、まずＣｕパターン線幅を測定し、次いでＣｕ選択性エッチング液（０．５質量％の過硫酸アンモニウム水溶液）にてＣｕパターンのみを溶解、除去したあと、ウエハ上に残ったＴｉ−Ｗパターン線幅をマイクロスコープで観察し測定した。Ｃｕパターン幅とその下部のＴｉ−Ｗパターン幅を比較することにより、アンダーカット量を測定した。
結果を表１に示す。
Undercut measurement was performed by first measuring the Cu pattern line width of the wafer after etching the Ti-W thin film, and then dissolving only the Cu pattern with a Cu selective etching solution (0.5% by mass ammonium persulfate aqueous solution). After removal, the Ti-W pattern line width remaining on the wafer was observed and measured with a microscope. The undercut amount was measured by comparing the Cu pattern width with the Ti-W pattern width underneath.
The results are shown in Table 1.
表１に示されるように、本発明のアルカリ性域のエッチング剤（実施例１〜４）は、比較例２と対比してエッチング速度が速いと共に、Ｃｕパターン表面の変色が無く、アンダーカット量が少なかった。本発明の酸性域のエッチング剤（実施例５〜１１）は、比較例１と対比してＣｕパターン表面の変色を防止できると共に、アンダーカット量が少なく、エッチング速度が速かった。すなわち、本発明のエッチング剤は、(i)Ｃｕパターン表面や無電解Ｎｉメッキ部に酸化・変色させない、(ii)Ｃｕパターン下のアンダーカットを極力抑制する、(iii)Ｔｉ及び／又はＷを含有する薄膜を短時間で選択的にエッチングすることができる優れたものであった。 As shown in Table 1, the etching agent (Examples 1 to 4) in the alkaline region of the present invention has a higher etching rate as compared with Comparative Example 2, has no discoloration of the Cu pattern surface, and has an undercut amount. There were few. The acidic range etching agent of the present invention (Examples 5 to 11) was capable of preventing discoloration of the Cu pattern surface as compared with Comparative Example 1, and had a low undercut amount and a high etching rate. That is, the etching agent of the present invention (i) does not oxidize or discolor the Cu pattern surface or electroless Ni plating part, (ii) suppresses undercut under the Cu pattern as much as possible, (iii) Ti and / or W. It was excellent that the contained thin film could be selectively etched in a short time.
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| JP2009051904A (en) * | 2007-08-24 | 2009-03-12 | General Technology Kk | Oily inkjet ink |
| WO2009081884A1 (en) * | 2007-12-21 | 2009-07-02 | Wako Pure Chemical Industries, Ltd. | Etching agent, etching method and liquid for preparing etching agent |
| KR101550069B1 (en) | 2008-01-16 | 2015-09-03 | 멕크 가부시키가이샤 | Etching solution |
| KR20160029094A (en) | 2013-07-05 | 2016-03-14 | 와코 쥰야꾸 고교 가부시키가이샤 | Etching agent, etching method and etching agent preparation liquid |
| KR101656756B1 (en) * | 2015-07-21 | 2016-09-13 | 대구가톨릭대학교산학협력단 | Copper etchant and the etching method of cupper interconnection using the same |
| CN107201519A (en) * | 2017-05-18 | 2017-09-26 | 苏州晶瑞化学股份有限公司 | A kind of selective two-component etching solution of titanium |
| CN107604362A (en) * | 2017-09-14 | 2018-01-19 | 江阴江化微电子材料股份有限公司 | A kind of two-component selectivity titanium corrosive liquid and titanium caustic solution |
| KR101934299B1 (en) | 2017-08-01 | 2019-01-02 | 엘티씨에이엠 주식회사 | Ti etchant Composition for Undercut prevention of an redistribution layer and/or a multi layer |
| CN112522707A (en) * | 2020-11-20 | 2021-03-19 | 湖北兴福电子材料有限公司 | Tungsten etching solution with high selectivity ratio |
| CN114196956A (en) * | 2020-09-18 | 2022-03-18 | 珠海市丹尼尔电子科技有限公司 | Etching solution for titanium |
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| JP2009051904A (en) * | 2007-08-24 | 2009-03-12 | General Technology Kk | Oily inkjet ink |
| WO2009081884A1 (en) * | 2007-12-21 | 2009-07-02 | Wako Pure Chemical Industries, Ltd. | Etching agent, etching method and liquid for preparing etching agent |
| JP2012080128A (en) * | 2007-12-21 | 2012-04-19 | Wako Pure Chem Ind Ltd | Etching agent, etching method, and etching agent preparation liquid |
| US8513139B2 (en) | 2007-12-21 | 2013-08-20 | Wako Pure Chemical Industries, Ltd. | Etching agent, etching method and liquid for preparing etching agent |
| CN103258727A (en) * | 2007-12-21 | 2013-08-21 | 和光纯药工业株式会社 | Etching agent, etching method and liquid for preparing etching agent |
| JP5343858B2 (en) * | 2007-12-21 | 2013-11-13 | 和光純薬工業株式会社 | Etching agent, etching method and etching agent preparation liquid |
| US8871653B2 (en) | 2007-12-21 | 2014-10-28 | Wako Pure Chemical Industries, Ltd. | Etching agent, etching method and liquid for preparing etching agent |
| KR101550069B1 (en) | 2008-01-16 | 2015-09-03 | 멕크 가부시키가이샤 | Etching solution |
| KR20160029094A (en) | 2013-07-05 | 2016-03-14 | 와코 쥰야꾸 고교 가부시키가이샤 | Etching agent, etching method and etching agent preparation liquid |
| US9845538B2 (en) | 2013-07-05 | 2017-12-19 | Wako Pure Chemical Industries, Ltd. | Etching agent, etching method and etching agent preparation liquid |
| KR101656756B1 (en) * | 2015-07-21 | 2016-09-13 | 대구가톨릭대학교산학협력단 | Copper etchant and the etching method of cupper interconnection using the same |
| CN107201519A (en) * | 2017-05-18 | 2017-09-26 | 苏州晶瑞化学股份有限公司 | A kind of selective two-component etching solution of titanium |
| KR101934299B1 (en) | 2017-08-01 | 2019-01-02 | 엘티씨에이엠 주식회사 | Ti etchant Composition for Undercut prevention of an redistribution layer and/or a multi layer |
| CN107604362A (en) * | 2017-09-14 | 2018-01-19 | 江阴江化微电子材料股份有限公司 | A kind of two-component selectivity titanium corrosive liquid and titanium caustic solution |
| CN114196956A (en) * | 2020-09-18 | 2022-03-18 | 珠海市丹尼尔电子科技有限公司 | Etching solution for titanium |
| CN114196956B (en) * | 2020-09-18 | 2024-03-12 | 珠海市丹尼尔电子科技有限公司 | Etching solution for titanium |
| CN112522707A (en) * | 2020-11-20 | 2021-03-19 | 湖北兴福电子材料有限公司 | Tungsten etching solution with high selectivity ratio |
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