JP2008053374A - Etching composition for titanium and aluminum metal laminate film - Google Patents
Etching composition for titanium and aluminum metal laminate film Download PDFInfo
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- 238000005530 etching Methods 0.000 title claims abstract description 116
- 239000010936 titanium Substances 0.000 title claims abstract description 71
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 61
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 239000005001 laminate film Substances 0.000 title description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 57
- 239000002184 metal Substances 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 46
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000007800 oxidant agent Substances 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 24
- 239000000956 alloy Substances 0.000 claims abstract description 24
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 24
- 239000011521 glass Substances 0.000 claims abstract description 23
- -1 hexafluorosilicic acid Chemical compound 0.000 claims abstract description 22
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 16
- 239000004065 semiconductor Substances 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims description 21
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 18
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 8
- BNZCDZDLTIHJAC-UHFFFAOYSA-N 2-azaniumylethylazanium;sulfate Chemical compound NCC[NH3+].OS([O-])(=O)=O BNZCDZDLTIHJAC-UHFFFAOYSA-N 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- 239000012935 ammoniumperoxodisulfate Substances 0.000 claims description 6
- 239000004973 liquid crystal related substance Substances 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 5
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 5
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 5
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 238000004544 sputter deposition Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 53
- 239000010408 film Substances 0.000 description 34
- 229910001069 Ti alloy Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 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 description 8
- 229910000838 Al alloy Inorganic materials 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000005385 peroxodisulfate group Chemical group 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NILMKXZBKQLWCT-UHFFFAOYSA-N 2-methylpiperazin-1-amine Chemical compound CC1CNCCN1N NILMKXZBKQLWCT-UHFFFAOYSA-N 0.000 description 1
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- JTDPJYXDDYUJBS-UHFFFAOYSA-N quinoline-2-carbohydrazide Chemical compound C1=CC=CC2=NC(C(=O)NN)=CC=C21 JTDPJYXDDYUJBS-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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Abstract
【課題】 ガラス等の絶縁膜基板、シリコン基板および化合物半導体基板上にスパッタリング法により成膜したチタンまたはチタンを主成分とする合金からなる層と、アルミニウムまたはアルミニウムを主成分とする合金からなる層とを含む金属積層膜を下地の基板等にダメージを与えることなく、さらに、テーパー角度を３０〜９０度に抑制し、積層膜を一括にエッチング可能なエッチング液組成物を提供する。
【解決手段】 本発明のエッチング液組成物は、ヘキサフルオロケイ酸、ふっ化水素酸の金属塩またはアンモニウム塩、およびヘキサフルオロケイ酸の金属塩またはアンモニウム塩からなる群から選ばれた少なくとも1種のふっ素化合物と酸化剤とを含有する。
【選択図】 なし
PROBLEM TO BE SOLVED: To provide a layer made of titanium or an alloy containing titanium as a main component and an aluminum or alloy layer containing an aluminum as a main component formed on an insulating film substrate such as glass, a silicon substrate and a compound semiconductor substrate by a sputtering method. In addition, an etching solution composition capable of etching the laminated film in a lump is provided by suppressing the taper angle to 30 to 90 degrees without damaging the underlying substrate or the like.
The etching solution composition of the present invention is at least one selected from the group consisting of hexafluorosilicic acid, a metal salt or ammonium salt of hydrofluoric acid, and a metal salt or ammonium salt of hexafluorosilicic acid. A fluorine compound and an oxidizing agent.
[Selection figure] None
Description
本発明は、液晶ディスプレイのゲート、ソースおよびドレイン電極等に使用される金属積層膜のエッチング液組成物に関する。 The present invention relates to an etching solution composition for a metal laminated film used for gate, source and drain electrodes of a liquid crystal display.
アルミニウムまたはアルミニウムにネオジム、シリコン、銅等の不純物を添加した合金は安価で抵抗が非常に低いため、液晶ディスプレイのゲート、ソースおよびドレイン電極等の材料に使用される。 Aluminum or an alloy obtained by adding an impurity such as neodymium, silicon, or copper to aluminum is inexpensive and has very low resistance, and thus is used as a material for a gate, a source, and a drain electrode of a liquid crystal display.
しかし、アルミニウムまたはアルミニウム合金は下地膜であるガラス基板との密着性が若干悪いこと、薬液や熱により腐食され易いため、アルミニウムまたはアルミニウム合金の上部および／または下部にモリブデンまたはモリブデン合金の膜を用いて積層膜として電極材料に使用され、りん酸等を用いたエッチング液により、積層膜の一括エッチングを行っていた。 However, since aluminum or aluminum alloy has a slightly poor adhesion to the glass substrate as a base film and is easily corroded by chemicals or heat, a molybdenum or molybdenum alloy film is used above and / or below aluminum or aluminum alloy. The laminated film is used as an electrode material, and the laminated film is collectively etched with an etching solution using phosphoric acid or the like.
近年、モリブデンまたはモリブデン合金の価格が高騰していること、薬液や熱による腐食性の更なる改善が求められていること等を理由にチタンまたはチタン合金が注目されている。モリブデンエッチング用のりん酸等では、チタンまたはチタン合金のエッチングは不可能であり、半導体基板ではチタン−アルミニウム系の金属積層膜のエッチング方法としてハロゲン系ガスを用いたリアクティブ・イオン・エッチング（ＲＩＥ）等の乾式エッチングが行われている。ＲＩＥでは異方性エッチングによりテーパー形状を有る程度コントロールできるが、高価な真空装置や高周波発生装置が必要となり、コスト面で不利である。そのため、より安価で処理時間が低減できる一括エッチング液の開発が望まれている。 In recent years, titanium or a titanium alloy has attracted attention for the reason that the price of molybdenum or a molybdenum alloy is soaring and that further improvement in corrosivity due to chemicals or heat is required. Etching of titanium or titanium alloy is impossible with phosphoric acid or the like for molybdenum etching, and reactive ion etching (RIE) using a halogen-based gas as a method for etching a titanium-aluminum metal laminated film on a semiconductor substrate. ) Etc. are dry-etched. In RIE, the degree of taper shape can be controlled by anisotropic etching, but an expensive vacuum device or high-frequency generator is required, which is disadvantageous in terms of cost. Therefore, it is desired to develop a batch etching solution that is cheaper and can reduce the processing time.
一方、半導体装置の製造工程においてチタンを主成分とする金属薄膜をエッチングする場合、一般にふっ化水素酸系エッチング液を使用することが知られている（例えば、特許文献１）。また、アンモニア水−過酸化水素水を用いたエッチング液によりチタンもしくはチタン合金のエッチングが可能であることも知られている（例えば特許文献２）。
しかしながら、ふっ化水素酸系エッチング液は、下地のガラス基板、シリコン基板および化合物半導体基板に対しダメージを与えるため使用できない。また、アンモニア水−過酸化水素水を用いた場合、過酸化水素水の分解により気泡が発生し、気泡の基板への付着によりエッチングが不完全となったり、液寿命が短いことから使用が困難である。
On the other hand, it is generally known to use a hydrofluoric acid-based etching solution when etching a metal thin film containing titanium as a main component in a manufacturing process of a semiconductor device (for example, Patent Document 1). It is also known that titanium or a titanium alloy can be etched with an etching solution using ammonia water-hydrogen peroxide water (for example, Patent Document 2).
However, the hydrofluoric acid etching solution cannot be used because it damages the underlying glass substrate, silicon substrate, and compound semiconductor substrate. In addition, when ammonia water-hydrogen peroxide solution is used, bubbles are generated due to decomposition of the hydrogen peroxide solution, and etching is incomplete due to adhesion of the bubbles to the substrate, and it is difficult to use because the liquid life is short. It is.
この他、ガラス基板等のエッチング液として用いられる本発明とは用途が異なるが、装飾品や電子部品に用いられるチタンまたはチタン合金の表面スケール除去および平滑化を目的とするエッチング液として、過酸化水素、フッ化物、無機酸類およびフッ素系界面活性剤を必須成分とする組成物が開示されているものの（特許文献３）、チタンまたはチタンを主成分とする合金からなる層とアルミニウムまたはアルミニウムを主成分とする合金からなる層とを含む金属積層膜をエッチングすることについて教示するものではない。また、チタン層と銅層からなる金属積層膜のエッチング液として、ペルオキソ二硫酸塩とフッ化物を含有する水溶液が開示されているが（特許文献４）、アルミ層とチタン層からなる金属積層膜についてエッチングするものではない。 In addition, the use is different from the present invention used as an etching solution for glass substrates, etc., but as an etching solution for the purpose of removing and smoothing the surface scale of titanium or titanium alloy used in decorative products and electronic parts, a peroxidation is used. Although a composition containing hydrogen, fluoride, inorganic acids, and a fluorosurfactant as essential components is disclosed (Patent Document 3), a layer made of titanium or a titanium-based alloy and aluminum or aluminum are mainly used. It does not teach etching of a metal laminated film including a layer made of an alloy as a component. Further, an aqueous solution containing peroxodisulfate and fluoride has been disclosed as an etchant for a metal laminate film composed of a titanium layer and a copper layer (Patent Document 4), but a metal laminate film composed of an aluminum layer and a titanium layer. Not about to etch.
チタン−アルミニウム金属積層膜を一括してエッチングするエッチング液として、フッ酸、過ヨウ素酸および硫酸を含有するエッチング液が開示されている（特許文献５）。しかし、このエッチング液は金属積層膜の各金属膜を同一エッチングレートでエッチングするものであり、したがって、エッチング後のテーパー角度がほぼ９０度となる。最近、ゲート電極線上に形成されるソース電極線の断線、ゲート電極線とソース電極線との間の短絡等を防止するために、基板上の配線をテーパー状（テーパー角度が９０度未満）とすることがしばしば行われているが（特許文献６）、特許文献５に記載のエッチング液ではこのような目的に対応できない。また、かかるエッチング液はガラス基板にダメージを与えるという問題も有する。 An etching solution containing hydrofluoric acid, periodic acid and sulfuric acid has been disclosed as an etching solution for etching a titanium-aluminum metal laminated film in a lump (Patent Document 5). However, this etchant etches each metal film of the metal laminated film at the same etching rate, and therefore the taper angle after etching is approximately 90 degrees. Recently, in order to prevent disconnection of the source electrode line formed on the gate electrode line, short circuit between the gate electrode line and the source electrode line, the wiring on the substrate is tapered (taper angle is less than 90 degrees). However, the etching solution described in Patent Document 5 cannot cope with such a purpose. In addition, such an etching solution has a problem of damaging the glass substrate.
一般にエッチング液は、チタンまたはチタン合金に対するより、アルミニウムまたはアルミニウム合金対する方がエッチングレートが大きい。したがって、チタンまたはチタン合金からなる層とアルミニウムまたはアルミニウム合金からなる層とを含む金属積層膜、例えばチタンまたはチタン合金／アルミニウムまたはアルミニウム合金／チタンまたはチタン合金からなる３層構造の金属積層膜を一括してエッチングし、テーパー状にできるエッチング液はまだ知られていない。
すなわち本発明の課題は、上記問題点を解決したチタン−アルミニウム系金属積層膜を、一括エッチングし、テーパー状にすることができるエッチング液を提供することにある。 That is, an object of the present invention is to provide an etchant that can collectively etch a titanium-aluminum-based metal laminated film that solves the above-described problems into a tapered shape.
上記課題を解決するため鋭意検討する中で、ふっ化水素酸の金属塩またはアンモニウム塩、ヘキサフルオロケイ酸、ヘキサフルオロケイ酸の金属塩またはアンモニウム塩、テトラフルオロホウ酸およびテトラフルオロホウ酸の金属塩またはアンモニウム塩からなる群から選ばれた少なくとも1種のふっ素化合物と酸化剤を組み合わせたエッチング液が、チタンまたはチタンを主成分とする合金からなる層とアルミニウムまたはアルミニウムを主成分とする合金からなる層とを含む金属積層膜を好適に一括エッチングできることを見いだすに至り、更に研究を進めた結果、本発明を完成するに至った。
即ち、本発明は、チタンまたはチタンを主成分とする合金からなる層とアルミニウムまたはアルミニウムを主成分とする合金からなる層とを含む金属積層膜を一括エッチングするのに用いるエッチング液組成物であって、ふっ化水素酸の金属塩またはアンモニウム塩、ヘキサフルオロケイ酸、ヘキサフルオロケイ酸の金属塩またはアンモニウム塩、テトラフルオロホウ酸およびテトラフルオロホウ酸の金属塩またはアンモニウム塩からなる群から選ばれた少なくとも1種のふっ素化合物と酸化剤とを含有する、前記エッチング液組成物に関する。
In the intensive study to solve the above-mentioned problems, metal salt or ammonium salt of hydrofluoric acid, metal salt or ammonium salt of hexafluorosilicic acid, metal salt of hexafluorosilicic acid, metal of tetrafluoroboric acid and tetrafluoroboric acid An etching solution in which at least one fluorine compound selected from the group consisting of a salt or an ammonium salt and an oxidizing agent are combined includes a layer made of titanium or a titanium-based alloy and an aluminum or aluminum-based alloy. As a result of further research, the present inventors have completed the present invention.
That is, the present invention is an etching solution composition used for collectively etching a metal laminated film including a layer made of titanium or an alloy containing titanium as a main component and a layer made of aluminum or an alloy containing aluminum as a main component. Selected from the group consisting of metal salts or ammonium salts of hydrofluoric acid, hexafluorosilicic acid, metal salts or ammonium salts of hexafluorosilicic acid, metal salts or ammonium salts of tetrafluoroboric acid and tetrafluoroboric acid. In addition, the present invention relates to the etching solution composition comprising at least one fluorine compound and an oxidizing agent.
本発明はまた、構成原料としてふっ化水素酸の金属塩またはアンモニウム塩、ヘキサフルオロケイ酸、ヘキサフルオロケイ酸の金属塩またはアンモニウム塩、テトラフルオロホウ酸およびテトラフルオロホウ酸の金属塩またはアンモニウム塩からなる群から選ばれた少なくとも1種のふっ素化合物、酸化剤および水のみを使用してなる、前記エッチング液組成物に関する。
さらに本発明は、酸化剤が、硝酸、硝酸アンモニウム、硫酸アンモニウム、ペルオキソ二硫酸アンモニウム、ペルオキソ二硫酸カリウム、過塩素酸、過塩素酸アンモニウム、過塩素酸ナトリウム、過塩素酸カリウム、過ヨウ素酸、過ヨウ素酸ナトリウム、過ヨウ素酸カリウム、メタンスルホン酸、過酸化水素水、硫酸および硫酸エチレンジアミンの中から選ばれた少なくとも1種である、前記エッチング液組成物に関する。
The present invention also provides a metal salt or ammonium salt of hydrofluoric acid, a metal salt or ammonium salt of hexafluorosilicic acid, a metal salt or ammonium salt of hexafluorosilicic acid, a metal salt or ammonium salt of tetrafluoroboric acid and tetrafluoroboric acid as a constituent raw material. The present invention relates to the etching solution composition comprising only at least one fluorine compound selected from the group consisting of: an oxidizing agent and water.
Further, in the present invention, the oxidizing agent is nitric acid, ammonium nitrate, ammonium sulfate, ammonium peroxodisulfate, potassium peroxodisulfate, perchloric acid, ammonium perchlorate, sodium perchlorate, potassium perchlorate, periodic acid, periodic acid. The present invention relates to the above etching solution composition, which is at least one selected from sodium, potassium periodate, methanesulfonic acid, hydrogen peroxide, sulfuric acid, and ethylenediamine sulfate.
また本発明は、ふっ素化合物の濃度が、０．０１〜５質量％、酸化剤の濃度が０．１〜５０質量％である、前記エッチング液組成物に関する。
本発明は、また、酸化剤が、硝酸またはメタンスルホン酸である、前記エッチング液組成物に関する。
さらに本発明は、酸化剤として、硝酸アンモニウム、硫酸アンモニウム、ペルオキソ二硫酸アンモニウム、ペルオキソ二硫酸カリウム、過塩素酸、過塩素酸アンモニウム、過塩素酸ナトリウム、過塩素酸カリウム、過ヨウ素酸、過ヨウ素酸ナトリウム、過ヨウ素酸カリウム、過酸化水素水、硫酸および硫酸エチレンジアミンの中から選ばれた少なくとも1種をさらに含む前記エッチング液組成物に関する。
本発明はまた、アミド硫酸、酢酸および塩酸の中から選ばれる少なくとも１種をさらに含む、前記エッチング液組成物に関する。
The present invention also relates to the etching solution composition, wherein the concentration of the fluorine compound is 0.01 to 5% by mass and the concentration of the oxidizing agent is 0.1 to 50% by mass.
The present invention also relates to the etching solution composition, wherein the oxidizing agent is nitric acid or methanesulfonic acid.
Furthermore, the present invention provides ammonium nitrate, ammonium sulfate, ammonium peroxodisulfate, potassium peroxodisulfate, perchloric acid, ammonium perchlorate, sodium perchlorate, potassium perchlorate, periodic acid, sodium periodate, The present invention relates to the etching solution composition further comprising at least one selected from potassium periodate, aqueous hydrogen peroxide, sulfuric acid, and ethylenediamine sulfate.
The present invention also relates to the above-mentioned etching solution composition further comprising at least one selected from amidosulfuric acid, acetic acid and hydrochloric acid.
また本発明は、下地基板が、液晶ディスプレイ用ガラス基板である、前記エッチング液組成物に関する。
さらに本発明は、下地基板が、半導体装置用シリコン基板または化合物半導体基板である、前記エッチング液組成物に関する。
本発明はまた、チタンまたはチタンを主成分とする合金からなる層と、アルミニウムまたはアルミニウムを主成分とする合金からなる層とを含む金属積層膜のエッチング後のテーパー角度を、３０〜９０度の範囲で制御することが可能な、前記エッチング液組成物に関する。
また本発明は、テーパー角度を３０〜８５度の範囲で制御することが可能な、前記エッチング液組成物に関する。
Moreover, this invention relates to the said etching liquid composition whose base substrate is a glass substrate for liquid crystal displays.
Furthermore, the present invention relates to the etching solution composition, wherein the base substrate is a silicon substrate for a semiconductor device or a compound semiconductor substrate.
In the present invention, the taper angle after etching of the metal laminated film including titanium or a layer made of titanium or an alloy containing titanium as a main component and a layer made of aluminum or an alloy containing aluminum as a main component is set to 30 to 90 degrees. It is related with the said etching liquid composition which can be controlled in the range.
Moreover, this invention relates to the said etching liquid composition which can control a taper angle in the range of 30-85 degree | times.
以上のとおり、本発明のエッチング液組成物は、構成原料としてふっ化水素酸の金属塩またはアンモニウム塩、ヘキサフルオロケイ酸、ヘキサフルオロケイ酸の金属塩またはアンモニウム塩、テトラフルオロホウ酸およびテトラフルオロホウ酸の金属塩またはアンモニウム塩からなる群から選ばれた少なくとも１種のふっ素化合物および酸化剤を含有する。本発明のエッチング液組成物はかかる構成により、チタンまたはチタンを主成分とする合金からなる層と、アルミニウムまたはアルミニウムを主成分とする合金からなる層とを含む金属積層膜のエッチングにおいて、エッチングレートをＴｉ＞Ａｌとすることができ、それにより、例えばチタンまたはチタン合金／アルミニウムまたはアルミニウム合金／チタンまたはチタン合金からなる３層構造の金属積層膜においても一括エッチングによりテーパー状に形成することができる。 As described above, the etching solution composition of the present invention comprises, as a constituent material, a metal salt or ammonium salt of hydrofluoric acid, hexafluorosilicic acid, a metal salt or ammonium salt of hexafluorosilicic acid, tetrafluoroboric acid and tetrafluoro It contains at least one fluorine compound selected from the group consisting of metal salts or ammonium salts of boric acid and an oxidizing agent. With such a configuration, the etching solution composition of the present invention has an etching rate in etching a metal laminated film including titanium or a layer composed of titanium as a main component and a layer composed of aluminum or an alloy based on aluminum as a main component. Ti> Al so that, for example, a three-layered metal laminated film made of titanium or titanium alloy / aluminum or aluminum alloy / titanium or titanium alloy can be formed into a tapered shape by batch etching. .
本発明において、構成原料のふっ素化合物としてふっ化水素酸を用いると、ガラス基板にダメージを与えるため、本発明ではふっ化水素酸構成原料として用いない。酸化剤は所望するテーパー角度に応じて適宜選択または組み合わせることができる。例えば、テーパー角度を４０度以下に制御する場合は硝酸またはメタンスルホン酸を用い、テーパー角度を５０度以上に制御する場合はペルオキソ二硫酸塩等の酸化剤を用いる。また、硝酸またはメタンスルホン酸と他の酸化剤を組み合わせることにより、所望のテーパー角度に制御することもできる。 In the present invention, when hydrofluoric acid is used as the constituent fluorine compound, the glass substrate is damaged. Therefore, in the present invention, it is not used as the hydrofluoric acid constituent raw material. The oxidizing agent can be appropriately selected or combined depending on the desired taper angle. For example, nitric acid or methanesulfonic acid is used when the taper angle is controlled to 40 degrees or less, and an oxidizing agent such as peroxodisulfate is used when the taper angle is controlled to 50 degrees or more. Further, the desired taper angle can be controlled by combining nitric acid or methanesulfonic acid with another oxidizing agent.
本発明のエッチング液は、下地基板に悪影響を及ぼすことなく、チタンまたはチタンを主成分とする合金からなる層と、アルミニウムまたはアルミニウムを主成分とする合金からなる層とを含む金属積層膜を一括エッチングし、テーパー状にできるため、ゲート電極の被覆性を向上させ、高品質な製品の製造を可能にするとともに、経済性にも優れる。また、テーパー角度のコントロールも容易に行うことができる。 The etching solution of the present invention collectively forms a metal laminated film including a layer made of titanium or an alloy containing titanium as a main component and a layer made of aluminum or an alloy containing aluminum as a main component without adversely affecting the base substrate. Since it can be etched and tapered, the coverage of the gate electrode can be improved, and high-quality products can be manufactured, and the economy is excellent. Also, the taper angle can be easily controlled.
本発明のエッチング液組成物は、ふっ素化合物、酸化剤および水により構成される。
本発明のエッチング液に使用されるふっ素化合物は、本エッチング液の成分である酸化剤により酸化された金属積層膜上の酸化チタンを溶解することにより、主としてエッチングするものと考えられる。本発明のエッチング液に使用するふっ素化合物は、ふっ化水素酸の金属塩またはアンモニウム塩、ヘキサフルオロケイ酸、ヘキサフルオロケイ酸の金属塩またはアンモニウム塩、テトラフルオロホウ酸およびテトラフルオロホウ酸の金属塩またはアンモニウム塩からなる群から選ばれた少なくとも1種である。ふっ素化合物は、例えばふっ化アンモニウム、ふっ化カリウム、ふっ化カルシウム、ふっ化水素アンモニウム、ふっ化水素カリウム、ふっ化ナトリウム、ふっ化マグネシウム、ふっ化リチウム、ヘキサフルオロケイ酸、ヘキサフルオロケイ酸アンモニウム、ヘキサフルオロケイ酸ナトリウム、ヘキサフルオロケイ酸カリウム、テトラフルオロホウ酸、テトラフルオロホウ酸アンモニウム、テトラフルオロホウ酸ナトリウム、テトラフルオロホウ酸カリウム等が好ましく、特にふっ化アンモニウムまたはふっ化水素アンモニウムが好ましい。
The etching solution composition of the present invention comprises a fluorine compound, an oxidizing agent and water.
It is considered that the fluorine compound used in the etching solution of the present invention is mainly etched by dissolving titanium oxide on the metal laminated film oxidized by the oxidizing agent that is a component of the present etching solution. The fluorine compound used in the etching solution of the present invention is a metal salt or ammonium salt of hydrofluoric acid, a metal salt or ammonium salt of hexafluorosilicic acid, hexafluorosilicic acid, a metal of tetrafluoroboric acid or tetrafluoroboric acid. It is at least one selected from the group consisting of salts and ammonium salts. Examples of the fluorine compound include ammonium fluoride, potassium fluoride, calcium fluoride, ammonium hydrogen fluoride, potassium hydrogen fluoride, sodium fluoride, magnesium fluoride, lithium fluoride, hexafluorosilicic acid, ammonium hexafluorosilicate, Sodium hexafluorosilicate, potassium hexafluorosilicate, tetrafluoroboric acid, ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate and the like are preferable, and ammonium fluoride or ammonium hydrogen fluoride is particularly preferable.
また、本発明のエッチング液に使用する酸化剤は、金属積層膜上のチタンまたはチタン合金を酸化することにより、エッチング開始剤としての役割を担う。本発明のエッチング液に使用する酸化剤は、好ましくは硝酸、硝酸アンモニウム、硫酸アンモニウム、ペルオキソ二硫酸アンモニウム、ペルオキソ二硫酸カリウム、過塩素酸、過塩素酸アンモニウム、過塩素酸ナトリウム、過塩素酸カリウム、過ヨウ素酸、過ヨウ素酸ナトリウム、過ヨウ素酸カリウム、メタンスルホン酸、過酸化水素水、硫酸およびエチレンジアミン硫酸塩から選ばれた少なくとも1種であり、このうち硝酸、ペルオキソ二硫酸アンモニウム、メタンスルホン酸がより好ましい。
硫酸アンモニウム、硫酸エチレンジアミン以外の含窒素有機化合物硫酸塩、例えばピペラジン、１−（２−アミノエチル）ピペラジン、１−アミノーメチルピペラジン等の硫酸塩も酸化剤として使用できるが、入手性の点で硫酸アンモニウム、硫酸エチレンジアミンが好ましい。
硝酸またはメタンスルホン酸は、低濃度においてもテーパー角度を低く、例えば４０度以下とすることができるので特に好ましい。硝酸およびメタンスルホン酸以外の酸化剤は、テーパー角度を低減する効果は低いものの、レジストへのダメージが小さく、サイドエッチング量を制御することができるので好ましい。上記ふっ素化合物と、硝酸またはメタンスルホン酸を含むエッチング液は、テーパー角度を４０度以下に制御することが可能であり、さらに硝酸およびメタンスルホン酸以外の酸化剤、またはアミド硫酸、酢酸および塩酸から選択された少なくとも１種を加えることにより、テーパー角度を３０〜９０度、好ましくは３０度以上９０度未満、より好ましくは３０〜８５度、さらに好ましくは３０〜８０度の間で制御することができる。
本発明のエッチング液組成物として好ましい組み合わせとしては、ふっ化アンモニウムと硝酸、ふっ化アンモニウムとメタンスルホン酸の他、酸化剤を２種以上使用する組み合わせとして、ふっ化アンモニウムと硝酸および過塩素酸、ふっ化アンモニウムと硝酸および硫酸、ふっ化アンモニウムと硝酸、過塩素酸およびメタンスルホン酸、ふっ化アンモニウムと硝酸、過塩素酸および硫酸等が挙げられる。
又、基板との濡れ性を高める目的で、本エッチング液に、一般に使用されている界面活性剤や有機溶剤を添加しても良い。
Moreover, the oxidizing agent used for the etching liquid of this invention bears the role as an etching initiator by oxidizing the titanium or titanium alloy on a metal laminated film. The oxidizing agent used in the etching solution of the present invention is preferably nitric acid, ammonium nitrate, ammonium sulfate, ammonium peroxodisulfate, potassium peroxodisulfate, perchloric acid, ammonium perchlorate, sodium perchlorate, potassium perchlorate, periodate At least one selected from acids, sodium periodate, potassium periodate, methanesulfonic acid, hydrogen peroxide, sulfuric acid, and ethylenediamine sulfate, among which nitric acid, ammonium peroxodisulfate, and methanesulfonic acid are more preferable .
Nitrogen-containing organic compound sulfates other than ammonium sulfate and ethylenediamine sulfate such as sulfates such as piperazine, 1- (2-aminoethyl) piperazine, 1-amino-methylpiperazine can also be used as oxidizing agents. Ethylenediamine sulfate is preferred.
Nitric acid or methanesulfonic acid is particularly preferable because the taper angle is low even at low concentrations, for example, 40 degrees or less. Oxidizing agents other than nitric acid and methanesulfonic acid are preferable because the effect of reducing the taper angle is low, but damage to the resist is small and the amount of side etching can be controlled. The etching solution containing the above fluorine compound and nitric acid or methanesulfonic acid can control the taper angle to 40 degrees or less, and further from an oxidizing agent other than nitric acid and methanesulfonic acid, or amidosulfuric acid, acetic acid and hydrochloric acid. By adding at least one selected, the taper angle can be controlled between 30 and 90 degrees, preferably between 30 and less than 90 degrees, more preferably between 30 and 85 degrees, and even more preferably between 30 and 80 degrees. it can.
Preferred combinations for the etching solution composition of the present invention include ammonium fluoride and nitric acid, ammonium fluoride and methanesulfonic acid, and combinations using two or more oxidizing agents, such as ammonium fluoride, nitric acid and perchloric acid, Examples thereof include ammonium fluoride and nitric acid and sulfuric acid, ammonium fluoride and nitric acid, perchloric acid and methanesulfonic acid, ammonium fluoride and nitric acid, perchloric acid and sulfuric acid.
Further, for the purpose of improving the wettability with the substrate, a generally used surfactant or organic solvent may be added to the etching solution.
本発明のエッチング液は、ガラス基板等からなる絶縁基板上およびシリコン、化合物半導体基板上に例えばスパッタリング法により形成された、チタンまたはチタンを主成分とする合金からなる層と、アルミニウムまたはアルミニウムを主成分とする合金からなる層とを含む金属積層膜、例えば、チタン／アルミニウム、アルミニウム/チタン、チタン／アルミニウム／チタンからなる金属積層膜をエッチングするのに好適であり、該エッチング液のふっ素化合物の濃度は０．０１〜５質量％、好ましくは０．１〜１質量％、酸化剤の濃度は０．１〜５０質量％、好ましくは０．５〜１０質量％である。 The etching solution of the present invention is mainly composed of a layer made of titanium or a titanium-based alloy formed on a silicon substrate or a compound semiconductor substrate, for example, on an insulating substrate made of a glass substrate or the like, and aluminum or aluminum. It is suitable for etching a metal laminated film including a layer made of an alloy as a component, for example, a metal laminated film made of titanium / aluminum, aluminum / titanium, titanium / aluminum / titanium, and a fluorine compound of the etching solution The concentration is 0.01 to 5% by mass, preferably 0.1 to 1% by mass, and the concentration of the oxidizing agent is 0.1 to 50% by mass, preferably 0.5 to 10% by mass.
ふっ素化合物濃度が５質量％以下の場合、下地ガラスにダメージを与えず、また、チタンまたはチタンを主成分とする合金からなる層と、アルミニウムまたはアルミニウムを主成分とする合金からなる層とを含む金属積層膜のサイドエッチング量が抑制され、０．０１質量％以上の場合、チタンまたはチタン合金のエッチングむらが少なくなり、エッチング後の形状が良好となる。酸化剤の含量が５０質量％以下の場合、チタンまたはチタンを主成分とする合金からなる層と、アルミニウムまたはアルミニウムを主成分とする合金からなる層とを含む金属積層膜のサイドエッチング量が抑制され、また、レジストへのダメージも発生せず、０．１質量％以上の場合、チタンまたはチタン合金のエッチング速度がはやく効率的である。
また、テーパー角度を適宜制御するには、とくに３０〜９０度とするためには、硝酸またはメタンスルホン酸を単独で用いるか、硝酸またはメタンスルホン酸と他の酸化剤を適宜組み合わせることにより行う。この場合、硝酸またはメタンスルホン酸は、０．１〜３０質量％、特に０．５〜１５質量％とすることが好ましく、他の酸化剤は、０．１〜２０質量％、特に０．５〜１５質量％とすることが好ましい。
とくに、テーパー角度を４０度以下にするためには、硝酸またはメタンスルホン酸を用いることが好ましい。
また、アミド硫酸、酢酸および塩酸から選ばれる少なくとも１種をさらに含む場合は、これらの濃度は、０．０１〜１０質量％、特に０．５〜５質量％が好ましい。
When the fluorine compound concentration is 5% by mass or less, the base glass is not damaged, and includes a layer made of titanium or an alloy containing titanium as a main component and a layer made of aluminum or an alloy containing aluminum as a main component. When the amount of side etching of the metal laminated film is suppressed and the amount is 0.01% by mass or more, uneven etching of titanium or a titanium alloy is reduced, and the shape after etching becomes good. When the content of the oxidizing agent is 50% by mass or less, the amount of side etching of the metal laminated film including titanium or a layer made of titanium as a main component and a layer made of aluminum or an alloy containing aluminum as a main component is suppressed. Further, no damage is caused to the resist, and when it is 0.1% by mass or more, the etching rate of titanium or titanium alloy is fast and efficient.
In order to appropriately control the taper angle, in particular, in order to set it to 30 to 90 degrees, nitric acid or methanesulfonic acid is used alone, or nitric acid or methanesulfonic acid and another oxidizing agent are appropriately combined. In this case, nitric acid or methanesulfonic acid is preferably 0.1 to 30% by mass, particularly preferably 0.5 to 15% by mass, and the other oxidizing agent is 0.1 to 20% by mass, particularly 0.5%. It is preferable to set it as -15 mass%.
In particular, nitric acid or methanesulfonic acid is preferably used in order to make the taper angle 40 degrees or less.
Moreover, when at least 1 sort (s) chosen from an amide sulfuric acid, an acetic acid, and hydrochloric acid is further included, these density | concentrations are 0.01-10 mass%, Especially 0.5-5 mass% is preferable.
本発明のエッチング液がエッチングする金属積層膜の下地基板は、特に限定されないが、チタン、アルミニウム金属積層膜が液晶ディスプレイに用いる場合にはガラス基板が好ましく、半導体装置に用いる場合には、シリコン基板と化合物半導体基板が好ましい。
以下に、実施例と比較例を挙げて本発明を更に詳細に説明するが、本発明はこれら実施例に限定されるものでない。
The base substrate of the metal laminated film to be etched by the etching solution of the present invention is not particularly limited, but a glass substrate is preferable when the titanium and aluminum metal laminated film is used for a liquid crystal display, and a silicon substrate when used for a semiconductor device. And a compound semiconductor substrate are preferred.
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
実施例１〜２６
図１に示すように、ガラス基板（１）上にスパッタリング法によりチタン(７００Å)／アルミニウム(２５００Å)／チタン(２００Å)を成膜した基板を準備した。
次に、ガラス／チタン／アルミニウム／チタン金属積層膜上に、レジスト（４）を用いてパターニングし、表１に示す実施例１〜２６のエッチング液（各実施例に記載の成分を含有する水溶液）に浸漬した(エッチング温度３０℃)。その後、超純水で洗浄し、窒素ブローで乾燥後基板形状を電子顕微鏡により観察した。結果を表１に示す。
Examples 1-26
As shown in FIG. 1, a substrate in which titanium (700 mm) / aluminum (2500 mm) / titanium (200 mm) was formed on a glass substrate (1) by sputtering was prepared.
Next, on the glass / titanium / aluminum / titanium metal laminated film, patterning is performed using a resist (4), and the etching liquids of Examples 1 to 26 shown in Table 1 (aqueous solutions containing the components described in each Example) ) (Etching temperature 30 ° C.). Thereafter, the substrate was washed with ultrapure water, dried with nitrogen blow, and the substrate shape was observed with an electron microscope. The results are shown in Table 1.
比較例1〜２
ガラス基板上にスパッタリング法によって形成した実施例で用いたガラス／チタン／アルミニウム／チタンを表１の比較例１〜２の各成分からなるエッチング液に浸漬し、実施例と同様にして処理を行った。結果を表1に併せて示す。
The glass / titanium / aluminum / titanium used in the example formed on the glass substrate by the sputtering method was immersed in an etching solution composed of each component of Comparative Examples 1 and 2 in Table 1 and treated in the same manner as in the example. It was. The results are also shown in Table 1.
表１から明らかに、本発明のエッチング液を用いてエッチングすることにより、スパッタリング法によって形成されたチタン／アルミニウム／チタン積層膜を短時間で一括でエッチングすることができた。また、酸化剤を適宜選択することにより所望のテーパー角度に制御できることがわかる。 As is apparent from Table 1, the titanium / aluminum / titanium laminated film formed by the sputtering method could be etched in a short time by etching using the etching solution of the present invention. Moreover, it turns out that it can control to a desired taper angle by selecting an oxidizing agent suitably.
比較例３〜５
特許文献５に記載のエッチング液を追試する目的で以下の組成のエッチング液（水溶液）を調製した。
比較例３：ふっ化水素酸（０．３質量％）＋過ヨウ素酸（０．５質量％）＋硫酸（０．５４質量％）
比較例４：ふっ化水素酸（１５質量％）＋過ヨウ素酸（１．５質量％）＋硫酸（５．４質量％）
比較例５：ふっ化水素酸（０．０３質量％）＋過ヨウ素酸（０．０５質量％）＋硫酸（０．０６質量％）
Comparative Examples 3-5
For the purpose of following the etching solution described in Patent Document 5, an etching solution (aqueous solution) having the following composition was prepared.
Comparative Example 3: Hydrofluoric acid (0.3% by mass) + periodic acid (0.5% by mass) + sulfuric acid (0.54% by mass)
Comparative Example 4: Hydrofluoric acid (15% by mass) + periodic acid (1.5% by mass) + sulfuric acid (5.4% by mass)
Comparative Example 5: Hydrofluoric acid (0.03% by mass) + periodic acid (0.05% by mass) + sulfuric acid (0.06% by mass)
次に、Ａｌ板（Ａｌ単独系：２０×１０×０．１ｍｍ）、Ｔｉ板（Ｔｉ単独系：２０×１０×０．１ｍｍ）、これら２枚を接続したＡｌ／Ｔｉ接触基板（Ａｌ−Ｔｉ接触系）、およびガラス板(２０×１８×０．１ｍｍ)を用意した。これら4種の基板を比較例３および4のエッチング液にそれぞれ浸漬し、エッチング速度を測定した(エッチング温度３０℃)。結果を表２に示す。また、Ａｇ／ＡｇＣｌを参照電極、白金板を対極として比較例３のエッチング液中におけるチタン及びアルミニウムの電極電位を測定し、チタンとアルミニウムの電位差を求めた。 Next, an Al plate (Al single system: 20 × 10 × 0.1 mm), a Ti plate (Ti single system: 20 × 10 × 0.1 mm), and an Al / Ti contact substrate (Al—Ti) connecting these two plates. Contact system) and a glass plate (20 × 18 × 0.1 mm) were prepared. These four kinds of substrates were respectively immersed in the etching solutions of Comparative Examples 3 and 4, and the etching rate was measured (etching temperature 30 ° C.). The results are shown in Table 2. Further, the electrode potential of titanium and aluminum in the etching solution of Comparative Example 3 was measured using Ag / AgCl as a reference electrode and a platinum plate as a counter electrode, and the potential difference between titanium and aluminum was determined.
次に、ガラス基板上にスパッタリング法によりアルミニウム（１８００Å）およびチタン（９００Å）を順次製膜した基板（ガラス／Ａｌ／Ｔｉ基板）を用意し、比較例３〜５のエッチング液にそれぞれ浸漬し、金属膜が溶解してガラス素地が見えるまでの時間(ＪＥＴ：ジャストエッチングタイム)を確認した。さらにそれぞれＪＥＴの１．２５倍の時間で浸漬処理したときの積層膜のエッチング形状を観察した。その結果を表３に示す。 Next, a substrate (glass / Al / Ti substrate) in which aluminum (1800 mm) and titanium (900 mm) are sequentially formed on a glass substrate by a sputtering method is prepared and immersed in the etching solutions of Comparative Examples 3 to 5, respectively. The time (JET: just etching time) until the glass film was melted and the glass substrate was seen was confirmed. Furthermore, the etching shape of the laminated film when the immersion treatment was performed for 1.25 times the time of JET was observed. The results are shown in Table 3.
比較例３のエッチング液において、各金属板のエッチングレートの比較から特許文献５に記載のエッチング液のエッチレートはＴｉ＜＜Ａｌであることがわかる。異種金属積層膜の場合、電池効果により単独金属と接触系でエッチングレートが異なることがあるが、比較例３のエッチング液中では単独系、接触系でエッチングレートに大きな差は認められず、積層基板においてもエッチレートはＴｉ＜＜Ａｌであることがわかる。ＡｌとＴｉの電極電位測定から求められた電位差は４００ｍＶ以内であることが確認されたが、上層のＴｉ溶解後、下層のＡｌのエッチングが高速で進むため、エッチング形状はテーパー状にならず、ほぼ垂直であった。また、比較例４のエッチング液はガラス基板の浸食が激しく、ガラス／Ａｌ／Ｔｉ積層基板においても短時間のエッチングにより下地ガラスが浸食されて不透明化し、比較例５のエッチング液はエッチング速度が遅く、いずれも実用的ではない。 From the comparison of the etching rates of the metal plates in the etching solution of Comparative Example 3, it can be seen that the etching rate of the etching solution described in Patent Document 5 is Ti << Al. In the case of a dissimilar metal laminated film, the etching rate may differ between the single metal and the contact system due to the battery effect, but in the etching solution of Comparative Example 3, there is no significant difference in the etching rate between the single system and the contact system. It can be seen that the etch rate of the substrate is Ti << Al. The potential difference obtained from the measurement of the electrode potential of Al and Ti was confirmed to be within 400 mV, but the etching of the lower layer of Al proceeds at a high speed after dissolution of the upper layer of Ti, so the etching shape does not become tapered, It was almost vertical. In addition, the etching solution of Comparative Example 4 is severely eroded by the glass substrate, and even in the glass / Al / Ti laminated substrate, the underlying glass is eroded and becomes opaque by short-time etching, and the etching solution of Comparative Example 5 has a slow etching rate. Neither is practical.
本発明のエッチング液は、半導体装置ならびに液晶ディスプレイ等の電子装置の製造工程において、配線または電極等を形成する際の金属積層膜のエッチング液として使用することが可能である。 The etching solution of the present invention can be used as an etching solution for a metal laminate film in forming a wiring or an electrode in a manufacturing process of an electronic device such as a semiconductor device or a liquid crystal display.
（１）ガラス基板
（２）チタンまたはチタン合金膜
（３）アルミニウムまたはアルミニウム合金膜
（４）レジスト
（ａ）本願発明のエッチング液によりエッチングした後のゲート電極（略一様なテーパー形状と４０度以下のテーパー形状）
（ｂ）本願発明のエッチング液によりエッチングした後のソースまたはドレイン電極（９０度のテーパー角度）
(1) Glass substrate (2) Titanium or titanium alloy film (3) Aluminum or aluminum alloy film (4) Resist (a) Gate electrode after etching with the etching solution of the present invention (substantially uniform taper shape and 40 degrees The following taper shape)
(B) Source or drain electrode after etching with the etching solution of the present invention (taper angle of 90 degrees)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60224228A (en) * | 1984-04-20 | 1985-11-08 | Fujitsu Ltd | Manufacture of amorphous silicon thin film transistor |
| JP2001311954A (en) * | 2000-04-28 | 2001-11-09 | Hitachi Ltd | Liquid crystal display device and manufacturing method thereof |
| JP2004071920A (en) * | 2002-08-08 | 2004-03-04 | Internatl Business Mach Corp <Ibm> | Etchant, thin film transistor array substrate, manufacturing method of thin film transistor array substrate, and display unit |
| JP2007005656A (en) * | 2005-06-24 | 2007-01-11 | Mitsubishi Gas Chem Co Inc | Etching composition for metal material and method for manufacturing semiconductor device using the same |
| JP2007067367A (en) * | 2005-02-24 | 2007-03-15 | Kanto Chem Co Inc | Etching composition for titanium and aluminum metal laminate film |
-
2006
- 2006-08-23 JP JP2006226980A patent/JP5010873B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60224228A (en) * | 1984-04-20 | 1985-11-08 | Fujitsu Ltd | Manufacture of amorphous silicon thin film transistor |
| JP2001311954A (en) * | 2000-04-28 | 2001-11-09 | Hitachi Ltd | Liquid crystal display device and manufacturing method thereof |
| JP2004071920A (en) * | 2002-08-08 | 2004-03-04 | Internatl Business Mach Corp <Ibm> | Etchant, thin film transistor array substrate, manufacturing method of thin film transistor array substrate, and display unit |
| JP2007067367A (en) * | 2005-02-24 | 2007-03-15 | Kanto Chem Co Inc | Etching composition for titanium and aluminum metal laminate film |
| JP2007005656A (en) * | 2005-06-24 | 2007-01-11 | Mitsubishi Gas Chem Co Inc | Etching composition for metal material and method for manufacturing semiconductor device using the same |
Cited By (20)
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|---|---|---|---|---|
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| JP2009267115A (en) * | 2008-04-25 | 2009-11-12 | Mitsubishi Chemicals Corp | Etching method and producing method of substrate for semiconductor device |
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| WO2010095742A1 (en) * | 2009-02-23 | 2010-08-26 | 関東化学株式会社 | Etching solution compositions for metal laminate films |
| JP2010199121A (en) * | 2009-02-23 | 2010-09-09 | Kanto Chem Co Inc | Etching solution composition for metal laminate film |
| US9039915B2 (en) | 2009-02-23 | 2015-05-26 | Kanto Kagaku Kabushiki Kaisha | Etching solution compositions for metal laminate films |
| KR101122698B1 (en) | 2009-05-25 | 2012-03-09 | 한국기계연구원 | Etchant composition of nickle-based superalloy and method of etching the alloy |
| WO2011010872A3 (en) * | 2009-07-22 | 2011-04-21 | 동우 화인켐 주식회사 | Etchant composition for forming a metal line |
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| US8894876B2 (en) | 2010-04-20 | 2014-11-25 | Samsung Display Co., Ltd. | Etchant for electrode and method of fabricating thin film transistor array panel using the same |
| WO2014065138A1 (en) * | 2012-10-22 | 2014-05-01 | 富士フイルム株式会社 | Etchant, etching method using same, and semiconductor-element production method |
| JP2017502129A (en) * | 2013-12-11 | 2017-01-19 | フジフイルム エレクトロニック マテリアルズ ユー．エス．エー．， インコーポレイテッド | Cleaning formulations for removing surface residues |
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| JP7105084B2 (en) | 2018-03-30 | 2022-07-22 | ナガセケムテックス株式会社 | Etchant composition |
| CN112430815A (en) * | 2020-11-23 | 2021-03-02 | 南通卓力达金属科技有限公司 | Etching solution and preparation method and application thereof |
| CN116103653A (en) * | 2022-11-16 | 2023-05-12 | 苏州博洋化学股份有限公司 | A kind of titanium aluminum titanium etchant and preparation method thereof |
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