JP4528164B2 - Etching solution composition - Google Patents
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- JP4528164B2 JP4528164B2 JP2005069252A JP2005069252A JP4528164B2 JP 4528164 B2 JP4528164 B2 JP 4528164B2 JP 2005069252 A JP2005069252 A JP 2005069252A JP 2005069252 A JP2005069252 A JP 2005069252A JP 4528164 B2 JP4528164 B2 JP 4528164B2
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- 238000005530 etching Methods 0.000 title claims description 162
- 239000000203 mixture Substances 0.000 title claims description 85
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 108
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 57
- 229910017604 nitric acid Inorganic materials 0.000 claims description 57
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 54
- RMIODHQZRUFFFF-UHFFFAOYSA-N methoxyacetic acid Chemical compound COCC(O)=O RMIODHQZRUFFFF-UHFFFAOYSA-N 0.000 claims description 42
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 32
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 25
- 239000010409 thin film Substances 0.000 claims description 25
- -1 amine compound Chemical class 0.000 claims description 23
- 229910052709 silver Inorganic materials 0.000 claims description 22
- 239000004332 silver Substances 0.000 claims description 22
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 16
- 239000004471 Glycine Substances 0.000 claims description 16
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 9
- 235000003704 aspartic acid Nutrition 0.000 claims description 9
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 9
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 87
- 238000011156 evaluation Methods 0.000 description 21
- 238000012360 testing method Methods 0.000 description 20
- 239000002253 acid Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 238000003860 storage Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910002668 Pd-Cu Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- TVMUHOAONWHJBV-UHFFFAOYSA-N dehydroglycine Chemical compound OC(=O)C=N TVMUHOAONWHJBV-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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- 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
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- 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
-
- 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
- C23F1/30—Acidic compositions for etching other metallic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
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- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
- Thin Film Transistor (AREA)
Description
本発明は、半導体装置およびフラットパネルディスプレイ装置等の各種電子装置の製造工程において、金属薄膜および金属酸化物薄膜をエッチングする際に用いるエッチング液組成物に関する。 The present invention relates to an etching solution composition used for etching a metal thin film and a metal oxide thin film in a manufacturing process of various electronic devices such as a semiconductor device and a flat panel display device.
電子装置の製造において、各種の金属薄膜や金属酸化物薄膜が用いられるが、従来から半導体装置の配線材料として、また、液晶ディスプレイ装置の反射板または反射電極材料として、アルミニウムおよびアルミニウム合金が用いられてきた。
近年、液晶ディスプレイ装置の反射板または反射電極材料として銀または銀を主成分とする合金が、また、透明電極材料として酸化インジウム錫（ＩＴＯ）および酸化インジウム亜鉛（ＩＺＯ）が使用されている。これらの配線、反射板、反射電極あるいは透明電極等を形成する際に使用する金属薄膜および金属酸化物薄膜のエッチング液組成物としては、アルミニウムおよびアルミニウム合金の金属薄膜の場合、従来からりん酸、硝酸、酢酸、水からなるエッチング液組成物(以下「混酸」と称する)が知られている。
Various metal thin films and metal oxide thin films are used in the manufacture of electronic devices. Conventionally, aluminum and aluminum alloys have been used as wiring materials for semiconductor devices and as reflectors or reflective electrode materials for liquid crystal display devices. I came.
In recent years, silver or an alloy containing silver as a main component is used as a reflective plate or a reflective electrode material of a liquid crystal display device, and indium tin oxide (ITO) and indium zinc oxide (IZO) are used as a transparent electrode material. As an etching solution composition of a metal thin film and a metal oxide thin film used when forming these wiring, reflector, reflective electrode or transparent electrode, in the case of a metal thin film of aluminum and aluminum alloy, phosphoric acid, An etchant composition (hereinafter referred to as “mixed acid”) comprising nitric acid, acetic acid and water is known.
一方、銀を主成分とする金属薄膜の場合、アルミニウムおよびアルミニウム合金のエッチング液として用いられている混酸をそのまま用いると、エッチングレートが高くなり、エッチングの制御性が悪くなる場合があるため、混酸の組成成分比を銀系金属薄膜用に最適化したもの（特許文献１）およびＩＴＯあるいはＩＺＯと銀あるいはアルミニウム等の金属薄膜との積層膜の場合、混酸の組成成分比を該積層膜の一括エッチング用に最適化したもの（特許文献２）が本発明の出願人により特許出願されている。
また、銀系金属薄膜用として、混酸にエチレングリコールまたはグリセリンを添加してエッチングレートを最適化したものが開示されている（特許文献３）。
On the other hand, in the case of a metal thin film containing silver as a main component, if the mixed acid used as an etching solution for aluminum and aluminum alloy is used as it is, the etching rate may be increased and the controllability of etching may be deteriorated. In the case where the composition component ratio is optimized for a silver-based metal thin film (Patent Document 1) and the laminated film of ITO or IZO and a metal thin film such as silver or aluminum, the composition ratio of the mixed acid is collectively determined for the laminated film. An application optimized for etching (Patent Document 2) has been filed by the applicant of the present invention.
In addition, for silver-based metal thin films, an etching rate optimized by adding ethylene glycol or glycerin to a mixed acid is disclosed (Patent Document 3).
このように、混酸は金属薄膜および金属酸化物薄膜のエッチング液として報告ないし使用されている。混酸中の硝酸は主として被エッチング材料を酸化する働きを有し、酢酸は被エッチング材料への濡れ性を向上させるとともに、エッチングレートをコントロールする役割を担うものであり、混酸の組成成分比率によりエッチング促進剤として、また、減速剤としても作用する。このため、混酸は、その組成成分比率を最適化することにより、制御性の良いエッチングレートで、エッチングを進行させることができる優れたエッチング液である。
しかし、混酸中の酢酸が高い揮発性を有するため、エッチング処理中に液組成が変化してしまい、安定したエッチング性能が保てなくなるという問題の主要因ともなっており、また、その刺激臭により作業環境を悪化させるという問題も有している。
混酸と類似のエッチング液組成物としてフッ酸、硝酸、酢酸および水からなるものが報告されているが（特許文献４）、酢酸を含むことによる臭気の問題を同様に有するものであり、さらにエッチングレートをコントロールするために、過酸化水素水を添加する必要があり、操作が煩雑となる問題がある。
Thus, the mixed acid has been reported or used as an etching solution for metal thin films and metal oxide thin films. Nitric acid in the mixed acid mainly functions to oxidize the material to be etched, and acetic acid improves the wettability to the material to be etched and plays a role in controlling the etching rate. Etching depends on the composition ratio of the mixed acid. Acts as an accelerator and as a moderator. For this reason, the mixed acid is an excellent etching solution that can advance the etching at an etching rate with good controllability by optimizing the composition component ratio.
However, the acetic acid in the mixed acid has high volatility, so the liquid composition changes during the etching process, which is the main cause of the problem that the stable etching performance cannot be maintained. It also has the problem of deteriorating the environment.
A composition composed of hydrofluoric acid, nitric acid, acetic acid and water has been reported as an etching solution composition similar to the mixed acid (Patent Document 4), but also has the problem of odor due to containing acetic acid, and further etched. In order to control the rate, it is necessary to add a hydrogen peroxide solution, and there is a problem that the operation becomes complicated.
酢酸の臭気という問題を解決するために、混酸の組成成分から酢酸を除いた、即ち、りん酸および硝酸からなるエッチング液組成物も報告されているが、エッチングレートの保持等のために、エッチング液組成物に硝酸を適宜供給する（特許文献５）、エッチング液組成物中に過酸化水素または硝酸を適宜供給する（特許文献６）等の工程を要し、いずれも操作が煩雑であって実用性がない。また、りん酸および硝酸のみからなるエッチング液組成物は、濡れ性が低いため、エッチング残渣が生じる、サイドエッチングが進行するなどの問題があり、精細なパターンの処理には不向きである。
さらに、混酸の組成成分である酢酸の代わりにクエン酸を用いたエッチング液組成物が開示されているが（特許文献７）、クエン酸には濡れ性向上効果がないため、精細なパターンエッジ形状は得られない、エッチング残渣を生じるなどの問題を有している。また、同文献は、ＮＯｘの発生を抑制するために尿素を添加するエッチング液組成物について開示するが、尿素はエッチング液組成物に対する溶解度が比較的低く、また、添加によりエッチングレートを大幅に抑制するという問題を有している。
このように、酢酸の臭気の問題がなく、エッチング性能に優れ、また取り扱いが容易で実用的に優れたエッチング液組成物は今まで知られていない。
In order to solve the problem of acetic acid odor, an etching solution composition in which acetic acid is removed from the mixed acid composition component, ie, phosphoric acid and nitric acid has been reported. Nitric acid is appropriately supplied to the liquid composition (Patent Document 5), hydrogen peroxide or nitric acid is appropriately supplied to the etching liquid composition (Patent Document 6), and the operation is complicated. There is no practicality. In addition, an etchant composition composed only of phosphoric acid and nitric acid has low wettability, and thus has problems such as etching residues and side etching, and is not suitable for processing fine patterns.
Furthermore, although an etching solution composition using citric acid instead of acetic acid, which is a composition component of mixed acid, is disclosed (Patent Document 7), since citric acid has no effect of improving wettability, a fine pattern edge shape is disclosed. Cannot be obtained, and etching residue is generated. The same document discloses an etchant composition in which urea is added to suppress the generation of NOx, but urea has a relatively low solubility in the etchant composition, and the addition significantly suppresses the etching rate. Have the problem of
Thus, an etching solution composition that does not have a problem of odor of acetic acid, has excellent etching performance, is easy to handle and is practically excellent has not been known so far.
すなわち本発明の課題は、半導体装置およびフラットパネルディスプレイ装置等の各種電子装置の製造工程において、金属薄膜をエッチングする際に用いることができるエッチング液組成物であって、臭気の問題がなく、かつ、安定したエッチング性能を維持できる、エッチング液組成物を提供することにある。 That is, an object of the present invention is an etching solution composition that can be used when etching a metal thin film in a manufacturing process of various electronic devices such as a semiconductor device and a flat panel display device, and has no odor problem. An object of the present invention is to provide an etching solution composition capable of maintaining stable etching performance.
上記課題を解決するため鋭意検討する中で、りん酸および硝酸に対する安定性および混和性等を有し、かつ臭気の問題がなく、さらにりん酸および硝酸に配合した時、混酸と少なくとも同等のエッチング性能を付与できる有機酸を使用するエッチング液組成物、即ち、酢酸以外の有機酸と、りん酸および硝酸を配合してなるエッチング液組成物が本課題を解決する手段となり得ることに着目した。 In an intensive study to solve the above problems, there is no problem of odor with stability and miscibility with phosphoric acid and nitric acid, and when mixed with phosphoric acid and nitric acid, etching at least equivalent to mixed acid It was noted that an etching solution composition using an organic acid capable of imparting performance, that is, an etching solution composition comprising an organic acid other than acetic acid, phosphoric acid and nitric acid can be a means for solving this problem.
それら有機酸の中でメトキシ酢酸は、りん酸および硝酸に任意の割合で混合でき、また、刺激臭がなく、常温で液体であるため、エッチング槽の液面付近および配管内で析出することなく、被エッチング物表面に対する濡れ性を高めることができ、かつ酢酸に匹敵するエッチングレート制御効果があることが確認され、りん酸、硝酸、メトキシ酢酸および水を配合してなる組成物が本課題を解決できるエッチング液組成物であることを見出すに至り、さらに研究を進めた結果、本発明を完成するに至った。 Among these organic acids, methoxyacetic acid can be mixed with phosphoric acid and nitric acid in any ratio, and since it has no irritating odor and is liquid at room temperature, it does not deposit near the liquid level in the etching tank or in the piping. It has been confirmed that the wettability to the surface of the object to be etched can be improved and that the etching rate control effect is comparable to that of acetic acid, and a composition comprising phosphoric acid, nitric acid, methoxyacetic acid and water has this problem. As a result of finding the etching solution composition that can be solved, and further research, the present invention has been completed.
すなわち、本発明は、金属薄膜をエッチングするエッチング液組成物であって、りん酸、硝酸、メトキシ酢酸および水を含有する、前記エッチング液組成物に関する。
また、本発明は、アミン化合物がさらに配合された、前記エッチング液組成物に関する。
さらに、本発明は、アミン化合物が、グリシン、アスパラギン酸、イミノ二酢酸から選択される１種または２種以上である、前記エッチング液組成物に関する。
また、本発明は、金属薄膜が銀または銀合金薄膜である、前記エッチング液組成物に関する。
さらに、本発明は、りん酸４〜９ｍｏｌ／Ｌ、硝酸０．１〜２ｍｏｌ／Ｌ、メトキシ酢酸２〜７ｍｏｌ／Ｌ、および水を含有する、前記エッチング液組成物に関する。
また、本発明は、りん酸４〜９ｍｏｌ／Ｌ、硝酸０．１〜２ｍｏｌ／Ｌ、メトキシ酢酸２〜７ｍｏｌ／Ｌ、およびアミン化合物の１種または２種以上を、合計して０．０５〜１ｍｏｌ／Ｌ、および水を配合してなる、前記エッチング液組成物に関する。
That is, the present invention relates to an etching solution composition for etching a metal thin film, which contains phosphoric acid, nitric acid, methoxyacetic acid and water.
The present invention also relates to the above-mentioned etching solution composition, which further contains an amine compound.
Furthermore, this invention relates to the said etching liquid composition whose amine compound is 1 type (s) or 2 or more types selected from glycine, aspartic acid, and iminodiacetic acid.
Moreover, this invention relates to the said etching liquid composition whose metal thin film is a silver or silver alloy thin film.
Furthermore, this invention relates to the said etching liquid composition containing phosphoric acid 4-9 mol / L, nitric acid 0.1-2 mol / L, methoxyacetic acid 2-7 mol / L, and water.
In addition, the present invention provides a total of 0.05 to 0.05 mol of phosphoric acid 4 to 9 mol / L, nitric acid 0.1 to 2 mol / L, methoxyacetic acid 2 to 7 mol / L, and one or more amine compounds. It is related with the said etching liquid composition formed by mix | blending 1 mol / L and water.
本発明のエッチング液組成物は、従来のエッチング液である混酸における組成成分の酢酸をメトキシ酢酸に代えた新規エッチング液組成物であり、刺激臭がなく、しかも、常温で液体であるメトキシ酢酸は、酢酸と同様に濡れ性を高める作用を有するため、該組成物はパターンエッジ形状等にも優れ、混酸と同等のエッチング性能を有する。また、従来の酢酸系では、酢酸揮発による成分変動のために安定した性能を維持できない傾向があるのに対し、本発明では、これに代えてメトキシ酢酸を用いているため、そのような問題がなく、液寿命が長い。
さらに、該組成物にグリシン等のアミン化合物を添加すると、エッチング処理後に密閉保管した際、あるいは短時間に多量のエッチング処理を行った際に、液が青く変色したり、発泡が生じたりするのを防止することができ、またエッチングレートの増大を抑制することができるため、その使用性は一層向上する。これは、系内に蓄積する過剰なＮＯｘ（とくにNO2 −）と反応するアミン化合物が、ＮＯｘ抑制効果を有することによるものと考えられる。
The etching solution composition of the present invention is a novel etching solution composition in which acetic acid as a composition component in a mixed acid that is a conventional etching solution is replaced with methoxyacetic acid, has no irritating odor, and is liquid at room temperature. Since it has the effect of increasing wettability like acetic acid, the composition is excellent in pattern edge shape and the like and has etching performance equivalent to that of mixed acid. In addition, in the conventional acetic acid system, there is a tendency that stable performance cannot be maintained due to component fluctuation due to volatilization of acetic acid, whereas in the present invention, methoxyacetic acid is used instead of this, so such a problem is caused. Long life of liquid.
Furthermore, when an amine compound such as glycine is added to the composition, the solution may turn blue or foam when stored in a sealed state after the etching process or when a large amount of etching process is performed in a short time. Can be prevented, and an increase in the etching rate can be suppressed, so that the usability is further improved. This is presumably because the amine compound that reacts with excess NOx (particularly NO 2 − ) accumulated in the system has a NOx suppressing effect.
以下に本発明の実施の形態について詳述する。
本発明のエッチング液組成物は、りん酸、硝酸、メトキシ酢酸および水を含有することを特徴とするものである。
Hereinafter, embodiments of the present invention will be described in detail.
The etching solution composition of the present invention contains phosphoric acid, nitric acid, methoxyacetic acid and water.
本発明のエッチング液組成物において、りん酸および硝酸の配合量はサイドエッチングが少なく、精度良くエッチング加工することができる範囲、とくにエッチングレート、エッチング残渣およびエッチングムラの発生などの観点から適宜決定する。エッチングレートが高い場合には、エッチング活性は良好であるが、エッチング反応時に多量の気泡が発生し、エッチングムラの原因になることがある。従って、エッチングする金属薄膜が銀または銀合金薄膜の場合、りん酸の配合量は好ましくは４〜９ｍｏｌ／Ｌ、より好ましくは５〜８ｍｏｌ／Ｌであり、硝酸の配合量は好ましくは０．１〜２ｍｏｌ／Ｌ、より好ましくは０．３〜１．５ｍｏｌ／Ｌである。一方、メトキシ酢酸の配合量は、エッチングレートを一定の範囲に保持することができ、エッチング残渣やパターンエッジ形状の凹凸等の問題も発生しない範囲とすることが好ましい。これらの観点からメトキシ酢酸の配合量は好ましくは２〜７ｍｏｌ／Ｌ、より好ましくは３〜６ｍｏｌ／Ｌである。 In the etching solution composition of the present invention, the blending amount of phosphoric acid and nitric acid is appropriately determined from the viewpoint of less side etching and accurate etching processing, particularly from the viewpoint of etching rate, etching residue, and etching unevenness. . When the etching rate is high, the etching activity is good, but a large amount of bubbles are generated during the etching reaction, which may cause etching unevenness. Therefore, when the metal thin film to be etched is a silver or silver alloy thin film, the amount of phosphoric acid is preferably 4 to 9 mol / L, more preferably 5 to 8 mol / L, and the amount of nitric acid is preferably 0.1. ˜2 mol / L, more preferably 0.3 to 1.5 mol / L. On the other hand, the amount of methoxyacetic acid is preferably in a range where the etching rate can be maintained within a certain range and problems such as etching residue and pattern edge shape unevenness do not occur. From these viewpoints, the amount of methoxyacetic acid is preferably 2 to 7 mol / L, more preferably 3 to 6 mol / L.
本発明のエッチング液組成物にはＮＯｘ抑制剤を適宜添加することができる。添加するＮＯｘ抑制剤は、ＮＯｘ抑制効果を有するものであれば特に限定されないが、アミン系化合物が好ましく、典型的には尿素、グリシン、アスパラギン酸およびイミノ二酢酸などが挙げられる。特に、りん酸、硝酸、メトキシ酢酸、および水を含む混酸への溶解性の高さや、エッチング阻害性の低さから、グリシン、アスパラギン酸およびイミノ二酢酸が好ましい。配合するアミン化合物は１種でも、また２種以上を組み合わせ配合してもよい。アミン化合物の組合せは、りん酸、硝酸、メトキシ酢酸および水に対する溶解性やエッチング阻害性等を考慮して適宜選択する。
アミン化合物の添加に際しては、ＮＯｘ抑制効果およびエッチングレートを考慮してその添加量を調整する。また、りん酸、硝酸、メトキシ酢酸および水の配合比によって、エッチング液組成物へのアミン化合物の溶解性が変動するので、この点も考慮の上添加量を調整することが好ましい。なお、銀エッチング量が多い場合には、アミン化合物を多く添加することが好ましい。
１種類のアミン化合物を使用する場合は、銀のエッチング量が４ｇ／Ｌのとき、グリシンは０．２ｍｏｌ／Ｌ以上、アスパラギン酸は０．１ｍｏｌ／Ｌ以上、イミノ二酢酸は０．０５ｍｏｌ／Ｌ以上の濃度でＮＯｘ抑制効果が認められる。また、これらのアミン化合物の上限は好ましくは１ｍｏｌ／Ｌ以下、より好ましくは０．５ｍｏｌ／Ｌ以下である。２種類以上のアミン化合物を使用する場合には、銀のエッチング量が４ｇ／Ｌの場合には、好ましくは０．０５〜１ｍｏｌ／Ｌ、より好ましくは０．１〜０．５ｍｏｌ／Ｌである。
A NOx inhibitor can be appropriately added to the etching solution composition of the present invention. The NOx inhibitor to be added is not particularly limited as long as it has a NOx suppressing effect, but is preferably an amine compound, and typically includes urea, glycine, aspartic acid, iminodiacetic acid, and the like. In particular, glycine, aspartic acid, and iminodiacetic acid are preferred because of their high solubility in mixed acids including phosphoric acid, nitric acid, methoxyacetic acid, and water, and low etching inhibition. The amine compound to mix | blend may be 1 type, and may mix | blend 2 or more types in combination. The combination of amine compounds is appropriately selected in consideration of solubility in phosphoric acid, nitric acid, methoxyacetic acid and water, etching inhibition properties, and the like.
When adding the amine compound, the addition amount is adjusted in consideration of the NOx suppressing effect and the etching rate. Further, since the solubility of the amine compound in the etching solution composition varies depending on the mixing ratio of phosphoric acid, nitric acid, methoxyacetic acid and water, it is preferable to adjust the addition amount in consideration of this point. In addition, when there is much silver etching amount, it is preferable to add many amine compounds.
When one kind of amine compound is used, when the etching amount of silver is 4 g / L, glycine is 0.2 mol / L or more, aspartic acid is 0.1 mol / L or more, and iminodiacetic acid is 0.05 mol / L. The NOx suppression effect is recognized at the above concentrations. Moreover, the upper limit of these amine compounds is preferably 1 mol / L or less, more preferably 0.5 mol / L or less. When two or more types of amine compounds are used, when the etching amount of silver is 4 g / L, it is preferably 0.05 to 1 mol / L, more preferably 0.1 to 0.5 mol / L. .
本発明のエッチング液組成物でエッチングを行う温度については、低温ではエッチングレートが低く、エッチング所用時間が長くなりすぎることがあり、一方高温ではエッチングレートが高く、エッチングの制御性が悪くなることなどを考慮し、その温度は、好ましくは２０〜４０℃である。 As for the temperature at which etching is performed with the etching solution composition of the present invention, the etching rate is low at low temperatures and the etching time may be too long, while the etching rate is high at high temperatures, resulting in poor etching controllability, etc. , The temperature is preferably 20-40 ° C.
さらに、被エッチング薄膜表面に対する濡れ性を改善するため、界面活性剤を含んでもよい。界面活性剤としてはノニオン系が望ましい。 Furthermore, in order to improve the wettability with respect to the surface of the thin film to be etched, a surfactant may be included. As the surfactant, a nonionic system is desirable.
また、本発明のエッチング液組成物は、りん酸、硝酸、メトキシ酢酸、水の配合量を適宜選択することにより、アルミニウム、銀、銅、モリブデン、ニッケル等の金属およびそれぞれの金属を主成分とする合金並びにＩＴＯ、ＩＺＯ等の金属酸化物よりなる薄膜のエッチング液として使用することができる。ここで、銀を主成分とする合金とは、典型的には銀（Ａｇ）−パラジウム（Ｐｄ）、Ａｇ−Ｐｄ−銅（Ｃｕ）、またはＡｇ−ネオジウム（Ｎｄ）−Ｃｕである。
また、本発明のエッチング液組成物は、アミン化合物の種類および配合量を適宜選択して配合することにより、ＮＯｘの過剰な発生を抑制することができる。
In addition, the etching solution composition of the present invention is mainly composed of metals such as aluminum, silver, copper, molybdenum, nickel, and the respective metals by appropriately selecting the blending amounts of phosphoric acid, nitric acid, methoxyacetic acid, and water. It can be used as an etching solution for a thin film made of an alloy and a metal oxide such as ITO or IZO. Here, the alloy containing silver as a main component is typically silver (Ag) -palladium (Pd), Ag-Pd-copper (Cu), or Ag-neodymium (Nd) -Cu.
Moreover, the etching liquid composition of this invention can suppress the excessive generation | occurrence | production of NOx by selecting and mixing suitably the kind and compounding quantity of an amine compound.
以下に、実施例と比較例を挙げて本発明をさらに詳細に説明するが、これらは本発明を何ら限定するものではない。なお、以下に記載したエッチングレートは、同一液で複数回エッチング操作を行い、安定したエッチングレートに至った時の数値を採用した。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but these do not limit the present invention in any way. In addition, the etching rate described below employ | adopted the numerical value when etching operation was performed in multiple times with the same liquid and it reached the stable etching rate.
［評価試験１] メトキシ酢酸の効果
酢酸代替物としてのメトキシ酢酸の効果を確認するために、りん酸６．０ｍｏｌ／Ｌ、硝酸１．０ｍｏｌ／Ｌおよび水からなる組成と、ここに酢酸またはメトキシ酢酸を５．０ｍｏｌ／Ｌ添加した組成で、りん酸／硝酸系への溶解性、エッチングレート（被エッチング材料：純銀箔（２ｃｍ角、厚さ５０μｍ）、液温：３０℃、安定なエッチングレートに至った後１分間、無攪拌）等を比較した結果を表１に示す。
これにより、メトキシ酢酸は酢酸と同様のエッチングレート制御効果と、りん酸／硝酸系への良好な溶解性を有するとともに、刺激臭がない等の長所があることを確認した。
[Evaluation Test 1] Effect of methoxyacetic acid In order to confirm the effect of methoxyacetic acid as a substitute for acetic acid, a composition comprising phosphoric acid 6.0 mol / L, nitric acid 1.0 mol / L and water, and acetic acid or methoxy Composition with acetic acid added at 5.0 mol / L, solubility in phosphoric acid / nitric acid system, etching rate (material to be etched: pure silver foil (2 cm square, thickness 50 μm), liquid temperature: 30 ° C., stable etching rate Table 1 shows the results of comparison of 1 minute, no stirring, etc.
As a result, it was confirmed that methoxyacetic acid has the same etching rate control effect as acetic acid, good solubility in phosphoric acid / nitric acid system, and no irritating odor.
［評価試験２］ エッチング液組成物の液寿命
りん酸６．０ｍｏｌ／Ｌ、硝酸０．６ｍｏｌ／Ｌ、酢酸７．０ｍｏｌ／Ｌおよび水からなる組成（比較例３）と、りん酸６．０ｍｏｌ／Ｌ、硝酸０．９ｍｏｌ／Ｌ、メトキシ酢酸５．０ｍｏｌ／Ｌおよび水からなる組成（実施例２）を用いて、液温３０℃、弱撹拌条件にて２４時間開放放置し、８時間ごとに各組成の成分をキャピラリー電気泳動法にて分析した結果を、表３および図１、２に示す。
りん酸／硝酸／酢酸系では、酢酸は揮発により大幅に減少し、りん酸および硝酸は大幅に濃縮される。りん酸／硝酸／酢酸系は、大幅な成分変動により初期性能を維持できず、長期使用が不可能なことは明白である。
これに対し、りん酸／硝酸／メトキシ酢酸系では、若干の濃縮傾向はあるものの、前記りん酸／硝酸／酢酸系に比べれば変動は軽微である。各成分が若干濃縮されているのは、主に水分揮発に起因するもので、水を補給すれば回復可能である。このように、りん酸／硝酸／メトキシ酢酸系は、従来のりん酸／硝酸／酢酸系に比べて、開放放置時の成分変動が少なく、長期使用に適した組成であることを確認した。
In the phosphoric acid / nitric acid / acetic acid system, acetic acid is greatly reduced by volatilization, and phosphoric acid and nitric acid are greatly concentrated. It is obvious that the phosphoric acid / nitric acid / acetic acid system cannot maintain the initial performance due to a large component variation and cannot be used for a long time.
On the other hand, in the phosphoric acid / nitric acid / methoxyacetic acid system, although there is a slight concentration tendency, the fluctuation is slight compared with the phosphoric acid / nitric acid / acetic acid system. The reason why each component is slightly concentrated is mainly due to moisture volatilization and can be recovered by replenishing water. As described above, it was confirmed that the phosphoric acid / nitric acid / methoxyacetic acid system had a smaller component fluctuation when left open than the conventional phosphoric acid / nitric acid / acetic acid system, and was suitable for long-term use.
［評価試験３］ エッチング液組成物の加工性能
りん酸７．０ｍｏｌ／Ｌ、硝酸０．５ｍｏｌ／Ｌおよび水からなる組成（比較例４）と、ここに酢酸またはメトキシ酢酸を５．０ｍｏｌ／Ｌ添加した組成（比較例５、および実施例３）にて、液温３０℃、安定なエッチングレートに至った後１分間、無攪拌条件で純銀箔（２ｃｍ角、厚さ５０μｍ）のエッチングレートを測定した。また、膜厚２００ｎｍの銀合金（Ａｇ−Ｐｄ−Ｃｕ）膜上に、レジストパターンを形成したガラス基板を準備し、前記３種のエッチング液組成物を用いて、液温３０℃、安定なエッチングレートに至った後のジャストエッチング時間、無撹拌条件でエッチング処理を行った。これらの結果を表５に示す。
この結果、りん酸／硝酸系での純銀箔のエッチングレートは２４０ｎｍ／ｍｉｎ．であった。銀合金基板のエッチング状態は、サイドエッチングが４．０μｍと大きいうえ、パターンエッジ形状も粗く、不良であった。これに対して、りん酸／硝酸／酢酸系、りん酸／硝酸／メトキシ酢酸系では、純銀箔のエッチングレートはそれぞれ８５０ｎｍ／ｍｉｎ．、７００ｎｍ／ｍｉｎ．であり、銀合金基板のエッチング状態はサイドエッチングも少なく、パターンエッジ形状も滑らかな、良好なエッチング状態を得た。
このように、りん酸／硝酸系に、酢酸またはメトキシ酢酸を添加したエッチング液組成物では、無添加系に比べて、エッチングレートおよび銀合金基板のエッチング状態が向上すること、並びにメトキシ酢酸が酢酸と同等以上の添加効果を示すことを確認した。
As a result, the etching rate of pure silver foil in the phosphoric acid / nitric acid system was 240 nm / min. Met. The etching state of the silver alloy substrate was poor because side etching was as large as 4.0 μm and the pattern edge shape was rough. On the other hand, in the phosphoric acid / nitric acid / acetic acid system and phosphoric acid / nitric acid / methoxyacetic acid system, the etching rate of pure silver foil was 850 nm / min. 700 nm / min. As a result, the etching state of the silver alloy substrate was small and the side etching was small, and the pattern edge shape was smooth and a good etching state was obtained.
Thus, in the etching solution composition in which acetic acid or methoxyacetic acid is added to the phosphoric acid / nitric acid system, the etching rate and the etching state of the silver alloy substrate are improved as compared with the non-added system, and methoxyacetic acid is acetic acid. It was confirmed that the effect of addition was equal to or greater than.
[評価試験４] アミン化合物添加による効果
りん酸６．０ｍｏｌ／Ｌ、硝酸１．０ｍｏｌ／Ｌ、メトキシ酢酸５．０ｍｏｌ／Ｌおよび水からなる基本組成に、各アミン化合物を各種配合量で添加し、銀を４ｇ／Ｌ溶解した後に密封保管した際の液安定性を評価した。この結果を表６に示す。
１週間の密封保管後のエッチング液組成物の安定性は、グリシンを０．２ｍｏｌ／Ｌ、アスパラギン酸を０．１ｍｏｌ／Ｌ、イミノ二酢酸を０．０５ｍｏｌ／Ｌ添加することで良好となる。
[Evaluation Test 4] Effect of adding amine compound Each amine compound was added in various amounts to a basic composition composed of 6.0 mol / L phosphoric acid, 1.0 mol / L nitric acid, 5.0 mol / L methoxyacetic acid and water. The liquid stability when silver was dissolved in 4 g / L and stored hermetically was evaluated. The results are shown in Table 6.
The stability of the etching solution composition after sealed storage for 1 week is improved by adding 0.2 mol / L of glycine, 0.1 mol / L of aspartic acid, and 0.05 mol / L of iminodiacetic acid.
[評価試験５] アミン化合物がエッチングレートに与える影響
りん酸６．０ｍｏｌ／Ｌ、硝酸１．０ｍｏｌ／Ｌ、メトキシ酢酸５．０ｍｏｌ／Ｌおよび水からなる基本組成に、各アミン化合物を０．５ｍｏｌ／Ｌ添加した組成のエッチングレートについて、評価試験１と同一条件で評価した結果を表７に示す。
[Evaluation Test 5] Effect of Amine Compound on Etching Rate 0.5 mol of each amine compound was added to a basic composition consisting of 6.0 mol / L phosphoric acid, 1.0 mol / L nitric acid, 5.0 mol / L methoxyacetic acid and water. Table 7 shows the results of evaluating the etching rate of the composition added with / L under the same conditions as in Evaluation Test 1.
グリシン、アスパラギン酸、またはイミノ二酢酸を添加した実施例１０〜１２は、エッチングレートの大幅な低下がなく、実施例１と同等の好適なエッチングレートが得られた。 In Examples 10 to 12 to which glycine, aspartic acid, or iminodiacetic acid was added, there was no significant decrease in the etching rate, and a suitable etching rate equivalent to that in Example 1 was obtained.
[評価試験６] 硝酸の濃度範囲
りん酸６．０ｍｏｌ／Ｌ、メトキシ酢酸５．０ｍｏｌ／Ｌ、グリシン０．２ｍｏｌ／Ｌに固定し、りん酸配合量を変更した組成におけるエッチングレートについて、評価試験１と同一条件で評価した結果を表８に示す。りん酸／硝酸／メトキシ酢酸／グリシン系のエッチングレートは、硝酸配合量によっても自由に調節が可能である。
[Evaluation Test 6] Concentration range of nitric acid Evaluation test for etching rate in a composition in which phosphoric acid was fixed at 6.0 mol / L, methoxyacetic acid 5.0 mol / L, glycine 0.2 mol / L, and the amount of phosphoric acid was changed Table 8 shows the results of evaluation under the same conditions as 1. The etching rate of phosphoric acid / nitric acid / methoxyacetic acid / glycine system can be freely adjusted by the nitric acid content.
［評価試験７] りん酸の濃度範囲
硝酸１．０ｍｏｌ／Ｌ、メトキシ酢酸５．０ｍｏｌ／Ｌ、グリシン０．２ｍｏｌ／Ｌに固定し、りん酸配合量を変更した組成におけるエッチングレートについて、評価試験１と同一条件で評価した結果を表９に示す。りん酸／硝酸／メトキシ酢酸／グリシン系のエッチングレートは、りん酸配合量により自由に調節が可能である。
[Evaluation Test 7] Phosphoric Acid Concentration Range Evaluation Test for Etching Rate in Composition with Fixed Nitric Acid 1.0mol / L, Methoxyacetic Acid 5.0mol / L, and Glycine 0.2mol / L Table 9 shows the results of evaluation under the same conditions as in Table 1. The etching rate of phosphoric acid / nitric acid / methoxyacetic acid / glycine system can be freely adjusted by the amount of phosphoric acid.
[評価試験８] メトキシ酢酸の濃度範囲
りん酸６．０ｍｏｌ／Ｌ、硝酸１．０ｍｏｌ／Ｌ、グリシン０．２ｍｏｌ／Ｌに固定し、メトキシ酢酸配合量を変更した組成におけるエッチングレートについて、評価試験１と同一条件で評価した結果を表１０に示す。りん酸／硝酸／メトキシ酢酸／グリシン系のエッチングレートは、メトキシ酢酸配合量によってもある程度調節できるが、その効果はりん酸または硝酸に比べると穏やかである。
[Evaluation Test 8] Concentration range of methoxyacetic acid Evaluation test for etching rate in a composition in which phosphoric acid was fixed at 6.0 mol / L, nitric acid 1.0 mol / L, glycine 0.2 mol / L, and the methoxyacetic acid compounding amount was changed. Table 10 shows the results of evaluation under the same conditions as in Table 1 . The etching rate of the phosphoric acid / nitric acid / methoxyacetic acid / glycine system can be adjusted to some extent by the amount of methoxyacetic acid, but the effect is milder than that of phosphoric acid or nitric acid.
[評価試験９] 銀、銀合金のエッチング
りん酸６．０ｍｏｌ／Ｌ、硝酸１．０ｍｏｌ／Ｌ、メトキシ酢酸５．０ｍｏｌ／Ｌ、グリシン０．２ｍｏｌ／Ｌ、および水からなる、実施例６のエッチング液組成物にて、液温３０℃、安定なエッチングレートに至った後１分間、無攪拌条件で純銀箔（２ｃｍ角、厚さ５０μｍ）のエッチングレートを測定したところ、エッチングレートは７６０ｎｍ／ｍｉｎ．であった。
膜厚２００ｎｍの銀合金（Ａｇ−Ｐｄ−Ｃｕ）膜上に、レジストパターンを形成したガラス基板を準備し、実施例６のエッチング液組成物を用いて、液温３０℃、安定なエッチングレートに至った後のジャストエッチング時間、無撹拌条件でエッチング処理を行った。
[Evaluation Test 9] Etching of Silver and Silver Alloy of Example 6 consisting of 6.0 mol / L phosphoric acid, 1.0 mol / L nitric acid, 5.0 mol / L methoxyacetic acid, 0.2 mol / L glycine, and water The etching rate of the pure silver foil (2 cm square, thickness 50 μm) was measured under the condition of no stirring for 1 minute after reaching a stable etching rate at a liquid temperature of 30 ° C. with the etching solution composition. min. Met.
A glass substrate on which a resist pattern is formed on a silver alloy (Ag—Pd—Cu) film having a thickness of 200 nm is prepared. Using the etching solution composition of Example 6, the liquid temperature is 30 ° C. and the etching rate is stable. Etching was performed under the conditions of just etching after the arrival and no stirring.
ジャストエッチング時間は光学顕微鏡にて、残渣がないことを確認して判定した。この結果、サイドエッチングが少なく、パターンエッジ形状も滑らかで、エッチング残渣もない、良好なエッチング状態を得た。 The just etching time was determined by confirming no residue with an optical microscope. As a result, a good etching state was obtained in which there was little side etching, the pattern edge shape was smooth, and there was no etching residue.
上記エッチング液組成物は、エッチング処理中および使用後の保管中にＮＯｘが発生することはなく、液安定性は良好であり、繰り返し使用可能であり、保存安定性が優れていた。 The etching solution composition did not generate NOx during the etching process and during storage after use, had good solution stability, could be used repeatedly, and had excellent storage stability.
[評価試験１０] 銀、銀合金のエッチング
りん酸６．０ｍｏｌ／Ｌ、硝酸１．０ｍｏｌ／Ｌ、メトキシ酢酸５．０ｍｏｌ／Ｌ、アスパラギン酸０．２ｍｏｌ／Ｌ、および水からなる、実施例６のエッチング液組成物を用いたこと以外は、評価試験９と同じ条件でエッチング試験を行った。
[Evaluation Test 10] Etching of silver and silver alloy Example 6 consisting of phosphoric acid 6.0 mol / L, nitric acid 1.0 mol / L, methoxyacetic acid 5.0 mol / L, aspartic acid 0.2 mol / L, and water The etching test was conducted under the same conditions as in the evaluation test 9 except that the etching solution composition was used.
この結果、純銀箔でのエッチングレートは８２０ｎｍ／ｍｉｎ．であった。銀合金／ガラス基板ではサイドエッチングが少なく、パターンエッジ形状も滑らかで、エッチング残渣もない、良好なエッチング状態を得た。 As a result, the etching rate with pure silver foil was 820 nm / min. Met. The silver alloy / glass substrate obtained a good etching state with little side etching, a smooth pattern edge shape, and no etching residue.
上記エッチング液組成物は、エッチング処理中および使用後の保管中にＮＯｘが発生することはなく、液安定性は良好であり、繰り返し使用可能であり、保存安定性が優れていた。 The etching solution composition did not generate NOx during the etching process and during storage after use, had good solution stability, could be used repeatedly, and had excellent storage stability.
[評価試験１１] 銀、銀合金のエッチング
りん酸６．０ｍｏｌ／Ｌ、硝酸１．０ｍｏｌ／Ｌ、メトキシ酢酸５．０ｍｏｌ／Ｌ、イミノ二酢酸０．２ｍｏｌ／Ｌ、および水からなる、実施例９のエッチング液組成物を用いたこと以外は、評価試験９と同じ条件でエッチング試験を行った。
[Evaluation Test 11] Etching of silver and silver alloy Examples comprising phosphoric acid 6.0 mol / L, nitric acid 1.0 mol / L, methoxyacetic acid 5.0 mol / L, iminodiacetic acid 0.2 mol / L, and water The etching test was performed under the same conditions as in the evaluation test 9 except that the etching solution composition of 9 was used.
この結果、純銀箔でのエッチングレートは６７０ｎｍ／ｍｉｎ．であった。銀合金／ガラス基板ではサイドエッチングが少なく、パターンエッジ形状も滑らかで、エッチング残渣もない、良好なエッチング状態を得た。 As a result, the etching rate with pure silver foil was 670 nm / min. Met. The silver alloy / glass substrate obtained a good etching state with little side etching, a smooth pattern edge shape, and no etching residue.
上記エッチング液組成物は、エッチング処理中および使用後の保管中にＮＯｘが発生することはなく、液安定性は良好であり、繰り返し使用可能であり、保存安定性が優れていた。 The etching solution composition did not generate NOx during the etching process and during storage after use, had good solution stability, could be used repeatedly, and had excellent storage stability.
上記銀、銀合金のエッチング評価試験より、りん酸、硝酸、メトキシ酢酸および水を配合してなるエッチング液組成物に、グリシン、アスパラギン酸、イミノニ酢酸から選択される１種または２種以上からなるアミノ化合物をさらに配合するエッチング液組成物は銀および銀合金に対して、良好なエッチング性能と液安定性を有することが確認された。 From the above-mentioned etching evaluation test of silver and silver alloys, the etching solution composition comprising phosphoric acid, nitric acid, methoxyacetic acid and water is composed of one or more selected from glycine, aspartic acid and iminoacetic acid. It was confirmed that the etching solution composition further blended with the amino compound has good etching performance and solution stability with respect to silver and silver alloys.
本発明によるエッチング液組成物は、半導体装置ならびにフラットパネルディスプレイ装置等の電子装置の製造工程において、配線、電極ならびに反射板等を形成する際の各種金属薄膜および金属酸化物薄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 composition according to the present invention is used as an etching solution for various metal thin films and metal oxide thin films when forming wirings, electrodes, reflectors, etc. in the manufacturing process of electronic devices such as semiconductor devices and flat panel display devices. Is possible.
Claims (5)
A total of 0.05 to 1 mol / L of phosphoric acid 4 to 9 mol / L, nitric acid 0.1 to 2 mol / L, methoxyacetic acid 2 to 7 mol / L, and one or more amine compounds, and water by blending the etchant composition according to claim 2-3.
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| TW095105030A TWI402330B (en) | 2005-03-11 | 2006-02-15 | Etching liquid composition |
| KR1020060022371A KR101299254B1 (en) | 2005-03-11 | 2006-03-09 | Etching liquid composition |
| CNB2006100547447A CN100543188C (en) | 2005-03-11 | 2006-03-10 | Etchant |
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| JP5158339B2 (en) * | 2007-12-11 | 2013-03-06 | 東ソー株式会社 | Etching composition and etching method |
| JP5228595B2 (en) * | 2008-04-21 | 2013-07-03 | ソニー株式会社 | SEMICONDUCTOR LIGHT EMITTING ELEMENT AND METHOD FOR MANUFACTURING SAME, LAMINATED STRUCTURE AND METHOD FOR FORMING THE SAME |
| KR101531688B1 (en) * | 2008-11-12 | 2015-06-26 | 솔브레인 주식회사 | Transparency etching solution |
| JP2010242124A (en) * | 2009-04-01 | 2010-10-28 | Tosoh Corp | Etching composition and etching method |
| JP6128847B2 (en) * | 2009-06-25 | 2017-05-17 | スリーエム イノベイティブ プロパティズ カンパニー | Wet etching method for self-assembled monolayer patterned substrate and metal patterned article |
| CN104630775B (en) * | 2015-02-15 | 2017-06-09 | 东南大学 | A kind of large-scale preparation method of heat exchanger aluminium foil fins set super hydrophobic surface |
| CN104893728B (en) * | 2015-04-10 | 2018-11-27 | 深圳新宙邦科技股份有限公司 | A kind of etching solution of the low-tension for ITO/Ag/ITO film |
| CN107099799A (en) * | 2017-03-31 | 2017-08-29 | 李世华 | A kind of chlorination copper etchant solution and preparation method thereof |
| CN112852429B (en) * | 2021-01-08 | 2022-09-09 | 绵阳艾萨斯电子材料有限公司 | Silver metal thin film layer etching solution and preparation and application thereof |
| JP7569252B2 (en) | 2021-03-26 | 2024-10-17 | 花王株式会社 | Method for storing etching solution composition |
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| WO2003031688A1 (en) * | 2001-10-09 | 2003-04-17 | Nagase Chemtex Corporation | Etchant composition |
| JP2004137586A (en) * | 2002-10-21 | 2004-05-13 | Mitsubishi Chemicals Corp | Etching liquid, and etching method |
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| JP2005206903A (en) * | 2004-01-23 | 2005-08-04 | Kanto Chem Co Inc | Etchant composition |
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| JP4668533B2 (en) * | 2001-07-06 | 2011-04-13 | サムスン エレクトロニクス カンパニー リミテッド | Etching solution for wiring, manufacturing method of wiring using the same, and manufacturing method of thin film transistor substrate including the same |
| KR100924479B1 (en) * | 2001-07-23 | 2009-11-03 | 소니 가부시끼 가이샤 | Etching Method and Etching Liquid |
| US20030168431A1 (en) * | 2002-02-25 | 2003-09-11 | Ritdisplay Corporation | Etchant composition for silver alloy |
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| WO2003031688A1 (en) * | 2001-10-09 | 2003-04-17 | Nagase Chemtex Corporation | Etchant composition |
| JP2004137586A (en) * | 2002-10-21 | 2004-05-13 | Mitsubishi Chemicals Corp | Etching liquid, and etching method |
| JP2004176115A (en) * | 2002-11-26 | 2004-06-24 | Kanto Chem Co Inc | Liquid composition for etching metallic thin film consisting essentially of silver |
| JP2004238656A (en) * | 2003-02-04 | 2004-08-26 | Kobe Steel Ltd | Etching liquid for silver thin film, and etching method and pattern forming method for silver thin film using the etching liquid |
| JP2005206903A (en) * | 2004-01-23 | 2005-08-04 | Kanto Chem Co Inc | Etchant composition |
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