JP6669566B2 - Silver etchant composition and display substrate using the same - Google Patents
Silver etchant composition and display substrate using the same Download PDFInfo
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- JP6669566B2 JP6669566B2 JP2016070480A JP2016070480A JP6669566B2 JP 6669566 B2 JP6669566 B2 JP 6669566B2 JP 2016070480 A JP2016070480 A JP 2016070480A JP 2016070480 A JP2016070480 A JP 2016070480A JP 6669566 B2 JP6669566 B2 JP 6669566B2
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 93
- 229910052709 silver Inorganic materials 0.000 title claims description 91
- 239000004332 silver Substances 0.000 title claims description 91
- 239000000203 mixture Substances 0.000 title claims description 65
- 239000000758 substrate Substances 0.000 title description 32
- 238000005530 etching Methods 0.000 claims description 94
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 3
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims 2
- 229910001195 gallium oxide Inorganic materials 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 claims 1
- 239000002356 single layer Substances 0.000 claims 1
- TYHJXGDMRRJCRY-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) tin(4+) Chemical compound [O-2].[Zn+2].[Sn+4].[In+3] TYHJXGDMRRJCRY-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 description 104
- 238000000034 method Methods 0.000 description 38
- 230000008569 process Effects 0.000 description 18
- 238000000151 deposition Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 229910045601 alloy Inorganic materials 0.000 description 13
- 239000000956 alloy Substances 0.000 description 13
- 230000008021 deposition Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 9
- 229920002120 photoresistant polymer Polymers 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000004544 sputter deposition Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- -1 azole compound Chemical class 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 239000002772 conduction electron Substances 0.000 description 6
- 229910052733 gallium Inorganic materials 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000008094 contradictory effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910021332 silicide Inorganic materials 0.000 description 3
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 150000003536 tetrazoles Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000599 controlled substance Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Electroluminescent Light Sources (AREA)
- ing And Chemical Polishing (AREA)
- Manufacturing & Machinery (AREA)
- Weting (AREA)
Description
本発明は、銀エッチング液組成物およびこれを用いた表示基板に関し、より詳細には、組成物の総重量に対して、リン酸３０〜６０重量％、硝酸０．５〜１０重量％、酢酸３３〜５０重量％、アゾール系化合物０．０１〜１０重量％、および組成物の総重量が１００重量％となるように残部の脱イオン水を含む銀エッチング液組成物およびこれを用いた表示基板に関する。 The present invention relates to a silver etchant composition and a display substrate using the same, and more specifically, 30 to 60% by weight of phosphoric acid, 0.5 to 10% by weight of nitric acid, and acetic acid, based on the total weight of the composition. Silver etchant composition containing 33 to 50% by weight, azole compound 0.01 to 10% by weight, and the remaining deionized water so that the total weight of the composition is 100% by weight, and display substrate using the same About.
本格的な情報化時代に入るにつれて大量の情報を処理および表示するディスプレイ分野が急速に発展してきており、これに応えて多様な平板ディスプレイが開発されて注目されている。 2. Description of the Related Art A display field for processing and displaying a large amount of information has been rapidly developed in a full-scale information age, and various flat panel displays have been developed and are receiving attention.
このような平板ディスプレイ装置の例としては、液晶ディスプレイ装置（Ｌｉｑｕｉｄ ｃｒｙｓｔａｌ ｄｉｓｐｌａｙ ｄｅｖｉｃｅ：ＬＣＤ）、プラズマディスプレイ装置（Ｐｌａｓｍａ Ｄｉｓｐｌａｙ Ｐａｎｅｌ ｄｅｖｉｃｅ：ＰＤＰ）、電界放出ディスプレイ装置（Ｆｉｅｌｄ Ｅｍｉｓｓｉｏｎ Ｄｉｓｐｌａｙ ｄｅｖｉｃｅ：ＦＥＤ）、エレクトロルミネッセンスディスプレイ装置（Ｅｌｅｃｔｒｏｌｕｍｉｎｅｓｃｅｎｃｅ Ｄｉｓｐｌａｙ ｄｅｖｉｃｅ：ＥＬＤ）、有機発光ディスプレイ（Ｏｒｇａｎｉｃ Ｌｉｇｈｔ Ｅｍｉｔｔｉｎｇ Ｄｉｏｄｅｓ：ＯＬＥＤ）などが挙げられる。また、このような平板ディスプレイ装置は、テレビやビデオなどの家電分野だけでなく、ノートパソコンのようなコンピュータおよび携帯電話などの多様な用途に用いられている。これらの平板ディスプレイ装置は、薄型化、軽量化、および低消費電力化などの優れた性能によって、既存に使用されていたブラウン管（Ｃａｔｈｏｄｅ Ｒａｙ Ｔｕｂｅ：ＮＩＴ）を素早く代替している。 Examples of such a flat panel display device include a liquid crystal display device (LCD), a plasma display device (Plasma Display Panel device: PDP), a field emission display device (Field Emission Display Device, and FED Sense). Examples include a display device (Electroluminescence Display device: ELD), an organic light emitting display (Organic Light Emitting Diodes: OLED), and the like. Further, such flat panel display devices are used not only in the field of home appliances such as televisions and videos, but also in various applications such as computers such as notebook computers and mobile phones. These flat panel display devices quickly replace the existing cathode ray tube (Cathode Ray Tube: NIT) due to excellent performance such as thinning, lightening, and low power consumption.
特に、ＯＬＥＤは、素子自体で光を発光し、低電圧でも駆動できるため、最近、携帯機器などの小型ディスプレイ市場に素早く適用されている。また、ＯＬＥＤは、小型ディスプレイを越えて、大型テレビの商用化を目前にしている状態である。 In particular, since OLEDs emit light by themselves and can be driven even at a low voltage, OLEDs have recently been rapidly applied to the market for small displays such as portable devices. In addition, OLEDs are moving beyond small displays to commercialize large televisions.
一方、酸化スズインジウム（Ｉｎｄｉｕｍ Ｔｉｎ Ｏｘｉｄｅ、ＩＴＯ）と酸化亜鉛インジウム（Ｉｎｄｉｕｍ Ｚｉｎｃ Ｏｘｉｄｅ、ＩＺＯ）のような導電性金属は、光に対する透過率が比較的優れ、導電性を有するので、平板ディスプレイ装置に用いられるカラーフィルタの電極に広く使用されている。しかし、これらの金属も、高い抵抗を有し、応答速度の改善による平板表示装置の大型化および高解像度の実現にハードルとなっている。 On the other hand, conductive metals, such as indium tin oxide (Indium Tin Oxide, ITO) and indium zinc oxide (Indium Zinc Oxide, IZO), have relatively excellent light transmittance and conductivity, so that they can be used in flat panel display devices. Widely used for electrodes of color filters used. However, these metals also have high resistance, which is a hurdle for realizing a large-sized flat panel display and realizing high resolution by improving the response speed.
また、反射板の場合、従来アルミニウム（Ａｌ）反射板を主に製品に用いてきた。しかし、輝度の向上による低電力消費実現のためには、反射率のより高い金属への材料変更を模索している状態である。このために、平板ディスプレイ装置に適用されている金属に比べて低い比抵抗と高い輝度を有する銀（Ａｇ：比抵抗約１．５９μΩｃｍ）膜、銀合金、またはこれを含む多層膜を、カラーフィルタの電極、ＬＣＤまたはＯＬＥＤ配線および反射板に適用、平板表示装置の大型化と高解像度および低電力消費などを実現すべく、該材料の適用のためのエッチング液の開発が要求された。 In the case of a reflection plate, an aluminum (Al) reflection plate has been mainly used for products conventionally. However, in order to realize low power consumption by improving the luminance, it is in a state of searching for a material change to a metal having a higher reflectance. To this end, a silver (Ag: specific resistance of about 1.59 μΩcm) film, a silver alloy, or a multilayer film including the same, which has a lower specific resistance and a higher luminance than a metal applied to a flat panel display device, is used as a color filter. The development of an etchant for application of such a material has been required in order to apply the material to electrodes, LCD or OLED wiring and reflectors, and to realize a large-sized flat panel display, high resolution, low power consumption, and the like.
しかし、銀（Ａｇ）は、ガラスなどの絶縁基板、または真性アモルファスシリコンやドーピングされたアモルファスシリコンなどからなる半導体基板などの下部基板に対して接着性（ａｄｈｅｓｉｏｎ）が極めて不良で蒸着が容易でなく、配線の浮き上がり（ｌｉｆｔｉｎｇ）または剥がれ（Ｐｅｅｌｉｎｇ）が誘発されやすい。また、銀（Ａｇ）導電層が基板に蒸着された場合にも、これをパターニングするためにエッチング液を使用する。このようなエッチング液として従来のエッチング液を使用する場合、銀（Ａｇ）が過度にエッチングされたり、不均一にエッチングされて配線の浮き上がりまたは剥がれ現象が発生し、配線の側面プロファイルが不良になる。特に、銀（Ａｇ）は還元されやすい金属で、エッチング速度が速くてこそ、残渣の誘発なくエッチングされることになるが、この時、エッチング速度が速くて上下部間のエッチング速度の差が発生せず、エッチング後のテーパ角（ｔａｐｅｒ ａｎｇｌｅ）の形成が難しく、配線への活用に多くの限界を持っている。金属膜がテーパ角（ｔａｐｅｒ ａｎｇｌｅ）なしに垂直に立っている場合、後続工程における絶縁膜または後続配線の形成時、銀（Ａｇ）と絶縁膜または配線との間に空隙が発生することがあり、このような空隙の発生は、電気的ショートなど、不良発生の原因となる。 However, silver (Ag) has an extremely poor adhesion to an insulating substrate such as glass or a lower substrate such as a semiconductor substrate made of intrinsic amorphous silicon or doped amorphous silicon, which makes deposition difficult. In addition, the lifting or peeling of the wiring is likely to be induced. Also, when a silver (Ag) conductive layer is deposited on a substrate, an etchant is used to pattern the silver (Ag) conductive layer. When a conventional etchant is used as such an etchant, silver (Ag) is excessively etched or non-uniformly etched, causing the wiring to lift or peel off, resulting in a poor side profile of the wiring. . In particular, silver (Ag) is a metal that can be easily reduced, and is etched without generating residues when the etching rate is high. At this time, the etching rate is high and a difference in the etching rate between the upper and lower parts occurs. Without this, it is difficult to form a taper angle after etching, and there are many limitations on utilization for wiring. When the metal film stands vertically without a taper angle, a gap may be generated between silver (Ag) and the insulating film or the wiring when the insulating film or the subsequent wiring is formed in a subsequent process. The generation of such a void causes a defect such as an electrical short.
一方、特許文献１に提示された銀エッチング液は、リン酸、硝酸、酢酸に、添加剤として補助酸化物溶解剤と含フッ素型炭素系界面活性剤を使用した。しかし、補助酸化物溶解剤として使用されたＳＯ４ ２−化合物は、銀（Ａｇ）と反応をして硫化銀（Ａｇ２Ｓ）の形態で基板内に残渣として残るという欠点があり、ＣｌＯ４ −化合物は、現在環境規制物質として規定されて使用に困難がある。また、前記組成物を用いて銀が含まれた金属膜をエッチングする場合、エッチング後のテーパ角（ｔａｐｅｒ ａｎｇｌｅ）の形成が難しい問題を依然として持っている。 On the other hand, the silver etching solution disclosed in Patent Document 1 uses an auxiliary oxide dissolving agent and a fluorinated carbon-based surfactant as additives in phosphoric acid, nitric acid, and acetic acid. However, SO 4 2-compounds used as auxiliary oxide solubilizer, it has the disadvantage of leaving as a residue in the substrate in the form of silver (Ag) and silver sulfide by the reaction (Ag 2 S), ClO 4 -The compounds are currently defined as environmentally controlled substances and are difficult to use. In addition, when etching a metal film containing silver using the composition, it is still difficult to form a taper angle after etching.
本発明は、銀を含む金属膜のエッチング後、テーパ角（ｔａｐｅｒ ａｎｇｌｅ）の形成を可能にする銀エッチング液組成物を提供することを目的とする。 SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver etchant composition capable of forming a taper angle after etching a metal film containing silver.
また、本発明は、前記銀エッチング液組成物を用いた表示基板および配線を提供することを目的とする。 Another object of the present invention is to provide a display substrate and a wiring using the silver etching solution composition.
上記の目的を達成するために、
本発明は、組成物の総重量に対して、リン酸３０〜６０重量％、硝酸０．５〜１０重量％、酢酸３３〜５０重量％、アゾール系化合物０．０１〜１０重量％、および組成物の総重量が１００重量％となるように残部の脱イオン水を含む銀エッチング液組成物を提供する。
To achieve the above objectives,
The present invention relates to a composition comprising 30 to 60% by weight of phosphoric acid, 0.5 to 10% by weight of nitric acid, 33 to 50% by weight of acetic acid, 0.01 to 10% by weight of an azole compound, and the composition, based on the total weight of the composition. Provided is a silver etchant composition containing the balance of deionized water so that the total weight of the product is 100% by weight.
また、本発明は、前記銀エッチング液組成物でエッチングされた金属膜を含む表示基板を提供する。 The present invention also provides a display substrate including a metal film etched with the silver etchant composition.
さらに、本発明は、前記銀エッチング液組成物でエッチングされた配線を提供する。 Further, the present invention provides a wiring etched with the silver etchant composition.
本発明の銀エッチング液組成物は、銀を含む金属膜のエッチング後、テーパ角（ｔａｐｅｒ ａｎｇｌｅ）の形成を可能にする。これによって、後続工程の進行に伴って後続の絶縁膜または配線が形成される時、テーパ角（ｔａｐｅｒ ａｎｇｌｅ）が四面に沿って緩やかに形成される効果を有する。 The silver etchant composition of the present invention allows for the formation of a taper angle after etching a metal film containing silver. Accordingly, when a subsequent insulating layer or a wiring is formed as a subsequent process proceeds, a taper angle is gradually formed along four surfaces.
以下、本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明は、銀エッチング液組成物の総重量に対して、リン酸３０〜６０重量％、硝酸０．５〜１０重量％、酢酸３３〜５０重量％、アゾール系化合物０．０１〜１０重量％、および組成物の総重量が１００重量％となるように残部の脱イオン水を含む銀エッチング液組成物に関する。本発明者は、前記のようなエッチング液組成物を用いて銀を含む金属膜をエッチングする場合、エッチング後のテーパ角（ｔａｐｅｒ ａｎｇｌｅ）の形成を可能にすることを、実験的に確認した。 According to the present invention, phosphoric acid is 30 to 60% by weight, nitric acid is 0.5 to 10% by weight, acetic acid is 33 to 50% by weight, and azole compound is 0.01 to 10% by weight based on the total weight of the silver etching solution composition. And a silver etchant composition comprising the balance of deionized water such that the total weight of the composition is 100% by weight. The present inventor has experimentally confirmed that a taper angle can be formed after etching when etching a metal film containing silver using the above-described etchant composition.
本発明の銀エッチング液組成物は、銀（Ａｇ）または銀合金からなる単一膜、または前記単一膜と透明導電膜とから構成される多層膜をエッチングできることが特徴であり、前記多層膜は同時にエッチング可能である。 The silver etchant composition of the present invention is characterized in that it can etch a single film made of silver (Ag) or a silver alloy, or a multilayer film composed of the single film and a transparent conductive film. Can be etched simultaneously.
前記銀合金は、銀を主成分とし、Ｉｎ、Ｐ、Ｎｄ、Ｃｕ、Ｐｄ、Ｎｂ、Ｎｉ、Ｍｏ、Ｎｉ、Ｃｒ、Ｍｇ、Ｗ、およびＴｉなどの他の金属を含む合金の形態と、銀の窒化物、ケイ化物、炭化物、および酸化物の形態などと多様であり得るが、これらに限定されるものではない。 The silver alloy has a form of an alloy containing silver as a main component and other metals such as In, P, Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W, and Ti; But may be, but not limited to, forms of nitride, silicide, carbide, and oxide.
また、前記透明導電膜は、一般的に、ＩＺＯとａ−ＩＴＯのように、可視光領域で透過率が約９０％以上であり、抵抗率が１×１０−４Ωｃｍ以下の特性を持っている。透明導電膜が透明であるためには、一般的に伝導電子が少なくなければならず、電気伝導度が大きくなるためには、伝導電子が多くなければならない。透明導電膜の場合、このように相反する２つの条件を満足しなければならない。ＩＺＯとａ−ＩＴＯを蒸着する方法には、一般的にスパッタリング（Ｓｐｕｔｔｅｒｉｎｇ）を用いるが、ＣＶＤ（Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ）方法に比べて蒸着条件を調節しやすく、大型の基板を用いて製造する場合、薄膜の厚さおよび薄膜特性の均一化を図るのに容易であるという利点がある。スパッタリング方法で製造する場合、酸化物ターゲットまたは合金ターゲット（ａｌｌｏｙ ｔａｒｇｅｔ）を使用する２つの方法があるが、合金ターゲットを使用する場合、蒸着速度が速く、ターゲット寿命もはるかに長く、ターゲット製造の容易性および再活用が可能であるという利点があるが、工程変数に敏感な特性変化を示すという欠点がある。酸化物ターゲットを用いると、薄膜の化学量論比を再現性あるように制御することができるが、合金ターゲットに比べて蒸着速度が遅く、蒸着途中にターゲットに物理的な亀裂が生じることがあり、ターゲットにアークが生じるという欠点がある。インジウム−主成分系酸化物をスパッタリングによって蒸着させる場合、Ｏ２と反応してＩｎ２Ｏ３の形態を有するが、電気伝導度を向上させるために、ドーパントとして、Ｇａ、Ｇｅ、Ｓｉ、Ｔｉ、Ｓｂ、Ｚｒ、Ｓｎ、およびＺｎなどを使用する。本発明において、ＩＴＯは、それぞれＩｎ２Ｏ３とＳｎＯ２が適正比率で混合されている透明導電膜を意味するが、これに限定されるものではない。例えば、ドーパントとして使用されるＧａとＺｎのみを用いて作ったＧＺＯの膜質なども適用可能である。さらに、前記多層膜は、透明導電膜／銀、透明導電膜／銀合金、透明導電膜／銀／透明導電膜、または透明導電膜／銀合金／透明導電膜で形成された多層膜であってもよいし、本発明の銀エッチング液組成物を使用する場合、下部膜を損傷させることなく、エッチング均一性を示すことができて、ウェットエッチングに有用に使用できる。 In addition, the transparent conductive film generally has a characteristic of having a transmittance of about 90% or more in a visible light region and a resistivity of 1 × 10 −4 Ωcm or less like IZO and a-ITO. I have. Generally, in order for the transparent conductive film to be transparent, the number of conduction electrons must be small, and in order to increase the electrical conductivity, the number of conduction electrons must be large. In the case of a transparent conductive film, these two contradictory conditions must be satisfied. In general, sputtering is used as a method for depositing IZO and a-ITO, but it is easier to adjust the deposition conditions than a CVD (Chemical Vapor Deposition) method, and when manufacturing using a large substrate, There is an advantage that it is easy to make the thickness and characteristics of the thin film uniform. When the sputtering method is used, there are two methods using an oxide target or an alloy target. However, when using an alloy target, the deposition rate is fast, the target life is much longer, and the target can be easily manufactured. It has the advantage that it can be reused and reused, but has the disadvantage of exhibiting property changes that are sensitive to process variables. When an oxide target is used, the stoichiometry of the thin film can be controlled with reproducibility, but the deposition rate is lower than that of an alloy target, and a physical crack may occur in the target during the deposition. However, there is a disadvantage that an arc is generated in the target. When the indium-based oxide is deposited by sputtering, it reacts with O 2 and has a form of In 2 O 3. In order to improve electrical conductivity, Ga, Ge, Si, Ti, Sb, Zr, Sn, Zn and the like are used. In the present invention, ITO means a transparent conductive film in which In 2 O 3 and SnO 2 are mixed at an appropriate ratio, but is not limited thereto. For example, a film quality of GZO made using only Ga and Zn used as a dopant is also applicable. Further, the multilayer film is a multilayer film formed of transparent conductive film / silver, transparent conductive film / silver alloy, transparent conductive film / silver / transparent conductive film, or transparent conductive film / silver alloy / transparent conductive film. Alternatively, when the silver etchant composition of the present invention is used, the uniformity of etching can be exhibited without damaging the lower film, and the silver etchant composition is useful for wet etching.
本発明の銀エッチング液組成物に含まれるリン酸（Ｈ３ＰＯ４）は主エッチング剤であって、単一膜または多層膜のエッチング時、銀（Ａｇ）または銀合金と酸化還元反応を起こし、透明導電膜を解離させてウェットエッチングする役割を果たす。 Phosphoric acid (H 3 PO 4 ) contained in the silver etchant composition of the present invention is a main etchant and causes an oxidation-reduction reaction with silver (Ag) or a silver alloy when etching a single film or a multilayer film. And performs the role of dissociating the transparent conductive film and performing wet etching.
前記リン酸は、銀エッチング液組成物の総重量に対して、３０〜６０重量％含まれ、好ましくは４０〜５０重量％含まれる。 The phosphoric acid is included in an amount of 30 to 60% by weight, preferably 40 to 50% by weight, based on the total weight of the silver etchant composition.
前記リン酸が３０重量％未満で含まれると、エッチング能力が不足して十分なエッチングが行われないことがある。また、工程の進行で一定量以上の銀（Ａｇ）が銀エッチング液組成物に溶解して入ると、銀（Ａｇ）再吸着または銀（Ａｇ）析出物が発生し、後続工程で電気的ショートを生じ得て、不良発生の原因となり得る。 If the content of the phosphoric acid is less than 30% by weight, the etching ability may be insufficient and sufficient etching may not be performed. Further, when a certain amount or more of silver (Ag) is dissolved into the silver etching solution composition during the process, silver (Ag) is re-adsorbed or silver (Ag) precipitate is generated, and an electrical short circuit occurs in a subsequent process. May occur, which may cause a failure.
前記リン酸が６０重量％を超える場合には、透明導電膜のエッチング速度は低下し、銀または銀合金のエッチング速度は過度に速くなって過剰エッチングが発生することがあり、これによって、配線の役割を果たせないだけのエッチング量が発生することがある。また、銀または銀合金に透明導電膜が積層された多層膜の場合、銀または銀合金と透明導電膜とのエッチング速度の差によるチップ（Ｔｉｐ）が発生し、後続工程に問題が発生することがある。 If the amount of phosphoric acid exceeds 60% by weight, the etching rate of the transparent conductive film decreases, and the etching rate of silver or silver alloy becomes excessively high, which may cause over-etching. In some cases, an etching amount that does not play a role is generated. Further, in the case of a multilayer film in which a transparent conductive film is laminated on silver or a silver alloy, a chip (Tip) is generated due to a difference in etching rate between the silver or silver alloy and the transparent conductive film, which causes a problem in a subsequent process. There is.
本発明の銀エッチング液組成物に含まれる硝酸（ＨＮＯ３）は、補助エッチング剤の役割を果たす成分で、単一膜または多層膜のエッチング時、銀（Ａｇ）または銀合金と透明導電膜を酸化させてウェットエッチングする役割を果たす。 Nitric acid (HNO 3 ) contained in the silver etchant composition of the present invention is a component that plays a role of an auxiliary etchant. When etching a single film or a multilayer film, silver (Ag) or a silver alloy and a transparent conductive film are used. It serves to oxidize and perform wet etching.
前記硝酸は、銀エッチング液組成物の総重量に対して、０．５〜１０重量％含まれ、好ましくは２〜１０重量％含まれる。 The nitric acid is contained in an amount of 0.5 to 10% by weight, preferably 2 to 10% by weight, based on the total weight of the silver etching solution composition.
前記硝酸の含有量が０．５重量％未満の場合には、銀または銀合金と透明導電膜のエッチング速度の低下が発生し、銀残渣によって、後続工程の進行に伴って電気的ショートおよび残渣の残っている領域が暗く見える現象である暗点不良が発生することがある。また、硝酸の含有量が１０重量％を超える場合には、過度のエッチング速度によって工程上エッチングの調節が難しく、過剰エッチングが発生して、配線としての役割を果たせなくなる。 If the content of the nitric acid is less than 0.5% by weight, the etching rate of the silver or silver alloy and the transparent conductive film decreases, and the silver residue causes an electric short circuit and a residue with the progress of the subsequent process. A dark spot defect, which is a phenomenon in which the remaining area looks dark, may occur. When the content of nitric acid exceeds 10% by weight, it is difficult to control the etching in the process due to an excessive etching rate, and excessive etching occurs, so that it cannot serve as a wiring.
本発明の銀エッチング液組成物に含まれる酢酸（ＣＨ３ＣＯＯＨ）は、反応速度などを調節するために緩衝制として作用し、それだけでなく、Ａｇ単一または合金がテーパ角（ｔａｐｅｒ ａｎｇｌｅ）を形成するのに非常に重要な役割を果たす。 Acetic acid (CH 3 COOH) contained in the silver etchant composition of the present invention acts as a buffer to control the reaction rate and the like. In addition, Ag alone or an alloy may have a taper angle. Plays a very important role in shaping.
前記酢酸は、銀エッチング液組成物の総重量に対して、３３〜５０重量％含まれる。 The acetic acid is included in an amount of 33 to 50% by weight based on the total weight of the silver etchant composition.
前記酢酸の含有量が３３重量％未満で含まれると、表示基板、より詳細には、ＴＦＴアレイ基板の配線のエッチング均一性が低下し、配線の直進性の低下で配線抵抗が大きくなったり、後続工程に不良を誘発することがあり、基板内のエッチング速度が不均一になって、基板上にシミが生じる問題が発生する。また、銀表面の湿潤性の低下によるフォトレジスト下端の浸透力低下によるテーパ角の形成されない問題が発生する。 When the acetic acid content is less than 33% by weight, the uniformity of the etching of the wiring of the display substrate, more specifically, the TFT array substrate is reduced, and the wiring resistance is increased due to the reduced linearity of the wiring. A defect may be induced in the subsequent process, and the etching rate in the substrate becomes non-uniform, which causes a problem that a stain occurs on the substrate. In addition, there is a problem that the taper angle is not formed due to a decrease in the penetrating power of the lower end of the photoresist due to a decrease in wettability of the silver surface.
また、前記酢酸の含有量が５０重量％を超えると、揮発性が非常に強い組成物になり、工程適用時、組成物の揮発によって３時間以内に組成物の含有量の変化が発生して、時間の経過とともにエッチング速度が変化する問題が発生する。 If the acetic acid content exceeds 50% by weight, the composition becomes very volatile, and during the application of the process, the content of the composition changes within 3 hours due to volatilization of the composition. This causes a problem that the etching rate changes with time.
本発明の銀エッチング液組成物に含まれるアゾール系化合物は、銀（Ａｇ）または銀合金のエッチング速度を遅くする役割をする腐食防止剤の役割を果たす成分であって、多層膜のエッチング時、相対的に透明導電膜の速度は遅くせず透明導電膜のチップ（Ｔｉｐ）の発生を制御し、工程上エッチング時間を調節することができる。また、銀（Ａｇ）の過剰エッチングを防止して狭い画素電極（Ｐｉｘｅｌ）の配線を形成することができて、パターンの微細な配線を形成するエッチング液組成物などに添加剤として使用できる。 The azole compound contained in the silver etchant composition of the present invention is a component that plays a role of a corrosion inhibitor that plays a role of reducing the etching rate of silver (Ag) or a silver alloy. It is possible to control the generation of the transparent conductive film tip without relatively slowing down the speed of the transparent conductive film and adjust the etching time in the process. Further, it is possible to form a wiring of a narrow pixel electrode (Pixel) by preventing over-etching of silver (Ag), and it can be used as an additive to an etching solution composition for forming a fine wiring of a pattern.
また、従来は、透明導電膜などのバリア（Ｂａｒｒｉｅｒ）膜がない銀または銀合金の単一膜をエッチング液組成物として用いてエッチングすると、過剰エッチングが発生した。これを防止するために、単一膜の上下部にバリア膜を適用したが、これは、工程上費用増加の原因となった。 Conventionally, when a single film of silver or a silver alloy without a barrier film such as a transparent conductive film is used as an etchant composition, excessive etching occurs. In order to prevent this, barrier films were applied to the upper and lower portions of the single film, but this caused an increase in cost in the process.
しかし、本発明の銀エッチング液組成物は、アゾール系化合物を使用することにより、過剰エッチングを予防可能でバリア膜を使用しなくてもよいし、それによって、工程時間の減少および原材料を節減することができて、生産費用を低減することができるという利点がある。 However, the silver etchant composition of the present invention can prevent over-etching and use no barrier film by using an azole-based compound, thereby reducing process time and saving raw materials. Therefore, there is an advantage that the production cost can be reduced.
本発明のアゾール系化合物は、テトラアゾール化合物であることが好ましく、具体的には、テトラゾール（Ｔｅｔｒａｚｏｌｅ、ＴＺ）、メチルテトラゾール（Ｍｅｔｈｙｌｔｅｔｒａｚｏｌｅ、ＭＴＺ）、およびアミノテトラゾール（Ａｍｉｎｏｔｅｔｒａｚｏｌｅ、ＡＴＺ）から選択される１つ以上であってもよい。最も好ましくは、メチルテトラゾール（Ｍｅｔｈｙｌｔｅｔｒａｚｏｌｅ、ＭＴＺ）であってもよい。 The azole compound of the present invention is preferably a tetraazole compound, and specifically, is selected from tetrazole (Tetrazole, TZ), methyltetrazole (Methyltetrazole, MTZ), and aminotetrazole (Aminotetrazole, ATZ) 1 There may be more than one. Most preferably, it may be methyltetrazole (MTZ).
前記アゾール系化合物は、銀エッチング液組成物の総重量に対して、０．０１〜１０重量％含まれる。前記アゾール系化合物の含有量が０．０１重量％未満であれば、エッチング速度を遅くする役割をまともに果たせず、微細なパターンを有するための配線形成時、過剰エッチングによる配線消失の不良が発生することがある。また、１０重量％を超えると、銀または銀合金のエッチング速度が著しく減少して不必要な部分が完全にエッチングされず電気的ショートを生じ得て、不良発生の原因となる。さらに、エッチング速度の低下によって残留物が残り、後続工程の進行後、製品生産時に一部領域が黒く見える暗点という不良現象を誘発することがある。 The azole compound is included in an amount of 0.01 to 10% by weight based on the total weight of the silver etchant composition. When the content of the azole compound is less than 0.01% by weight, it does not play a role of slowing down the etching rate, and when forming a wiring for forming a fine pattern, a failure of wiring disappearance due to excessive etching occurs. May be. On the other hand, if the content exceeds 10% by weight, the etching rate of silver or silver alloy is remarkably reduced, and unnecessary portions are not completely etched, which may cause an electric short circuit, thereby causing a defect. Furthermore, a residue may be left due to a decrease in the etching rate, which may cause a defective phenomenon such as a dark spot in which a part of the region looks black when a product is manufactured after a subsequent process is performed.
本発明の銀エッチング液組成物に含まれる脱イオン水は、半導体工程用を使用し、好ましくは１８ＭΩ／ｃｍ以上の水を使用する。 The deionized water contained in the silver etching solution composition of the present invention is used for a semiconductor process, and preferably, water of 18 MΩ / cm or more is used.
本発明の銀エッチング液組成物は、上記に言及された成分のほか、この分野で通常使用されるエッチング調節剤およびｐＨ調節剤のうちの１つ以上をさらに含むことができる。 The silver etchant composition of the present invention may further include, in addition to the above-mentioned components, one or more of an etch control agent and a pH control agent commonly used in the art.
前記追加的に含まれるエッチング調節剤としては、酢酸カリウムまたは酢酸ナトリウムのうちの１つの酢酸塩を含む化合物であり、追加的に含まれるｐＨ調節剤としては、グリコール酸、グルタミン酸、またはグリシンのうちの１つの有機酸を含む化合物である。 The additional etch control agent may be a compound containing an acetate of one of potassium acetate and sodium acetate, and the additional pH control agent may be glycolic acid, glutamic acid, or glycine. Is a compound containing one organic acid.
本発明の銀エッチング液組成物は、ディスプレイ（ＯＬＥＤ、ＬＣＤなど）のＴＦＴアレイ基板、ＴＳＰ Ｔｒａｃｅ配線、およびＦｌｅｘｉｂｌｅ用ナノワイヤ配線形成用に多く使用される透明導電膜、銀、銀合金を用いた単一膜、または２つ以上を使用した多層構造のエッチング液として使用できる。それだけでなく、前記明示されたディスプレイ、ＴＳＰ以外にも、半導体など、前記金属膜質を用いた電子部品素材に使用できる。 The silver etchant composition of the present invention is a transparent conductive film often used for forming a TFT array substrate of a display (such as an OLED or an LCD), a TSP trace wiring, and a nanowire wiring for a flexible, and a silver or silver alloy. It can be used as an etchant of a single film or a multilayer structure using two or more films. In addition to the above-mentioned display and TSP, the present invention can be used for an electronic component material using the metal film, such as a semiconductor.
また、本発明は、本発明の銀エッチング液組成物でエッチングされた金属膜を含む表示基板を提供することができる。 In addition, the present invention can provide a display substrate including a metal film etched with the silver etchant composition of the present invention.
より詳細には、前記表示装置は、液晶表示装置（ＬＣＤ）または有機発光素子（ＯＬＥＤ）の薄膜トランジスタ（ＴＦＴ）基板であってもよい。 More specifically, the display device may be a liquid crystal display (LCD) or a thin film transistor (TFT) substrate of an organic light emitting device (OLED).
また、前記ＯＬＥＤは、金属膜を上部および下部に積層することができ、本発明のエッチング液組成物で金属膜をエッチングすることができる。上部および下部に金属膜の厚さを調節して積層することにより、ＯＬＥＤにおいて、前記金属膜は、反射膜および半透過膜の役割を果たすことができる。 In addition, the OLED can be formed by laminating a metal film on an upper portion and a lower portion, and can etch the metal film with the etchant composition of the present invention. In the OLED, the metal film may function as a reflective film and a semi-transmissive film by adjusting and stacking the metal film on the upper and lower portions.
前記反射膜は、光がほとんど透過しない厚さでなければならず、前記半透過膜は、光がほとんど透過する厚さでなければならない。したがって、前記金属膜の厚さは、５０〜５０００Åであることが好ましい。 The reflective film must be thick enough to transmit little light, and the semi-transmissive film must be thick enough to transmit little light. Therefore, it is preferable that the thickness of the metal film is 50 to 5000 °.
前記金属膜は、銀（Ａｇ）または銀合金からなる単一膜、または前記単一膜と透明導電膜とから構成される多層膜である。 The metal film is a single film made of silver (Ag) or a silver alloy, or a multilayer film composed of the single film and a transparent conductive film.
前記銀合金は、銀を主成分とし、Ｉｎ、Ｐ、Ｎｄ、Ｃｕ、Ｐｄ、Ｎｂ、Ｎｉ、Ｍｏ、Ｎｉ、Ｃｒ、Ｍｇ、Ｗ、およびＴｉなどの他の金属を含む合金の形態と、銀の窒化物、ケイ化物、炭化物、および酸化物の形態などと多様であり得るが、これらに限定されるものではない。 The silver alloy has a form of an alloy containing silver as a main component and other metals such as In, P, Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W, and Ti; But may be, but not limited to, forms of nitride, silicide, carbide, and oxide.
また、前記透明導電膜は、一般的に、ＩＺＯとａ−ＩＴＯのように、可視光領域で透過率が約９０％以上であり、抵抗率が１×１０−４Ωｃｍ以下の特性を持っている。透明導電膜が透明であるためには、一般的に伝導電子が少なくなければならず、電気伝導度が大きくなるためには、伝導電子が多くなければならない。透明導電膜の場合、このように相反する２つの条件を満足しなければならない。ＩＺＯとａ−ＩＴＯを蒸着する方法には、一般的にスパッタリング（Ｓｐｕｔｔｅｒｉｎｇ）を用いるが、ＣＶＤ（Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ）方法に比べて蒸着条件を調節しやすく、大型の基板を用いて製造する場合、薄膜の厚さおよび薄膜特性の均一化を図るのに容易であるという利点がある。スパッタリング方法で製造する場合、酸化物ターゲットまたは合金ターゲット（ａｌｌｏｙ ｔａｒｇｅｔ）を使用する２つの方法があるが、合金ターゲットを使用する場合、蒸着速度が速く、ターゲット寿命もはるかに長く、ターゲット製造の容易性および再活用が可能であるという利点があるが、工程変数に敏感な特性変化を示すという欠点がある。酸化物ターゲットを用いると、薄膜の化学量論比を再現性あるように制御することができるが、合金ターゲットに比べて蒸着速度が遅く、蒸着途中にターゲットに物理的な亀裂が生じることがあり、ターゲットにアークが生じるという欠点がある。インジウム−主成分系酸化物をスパッタリングによって蒸着させる場合、Ｏ２と反応してＩｎ２Ｏ３の形態を有するが、電気伝導度を向上させるために、ドーパントとして、Ｇａ、Ｇｅ、Ｓｉ、Ｔｉ、Ｓｂ、Ｚｒ、Ｓｎ、およびＺｎなどを使用する。本発明において、ＩＴＯは、それぞれＩｎ２Ｏ３とＳｎＯ２が適正比率で混合されている透明導電膜を意味するが、これに限定されるものではない。例えば、ドーパントとして使用されるＧａとＺｎのみを用いて作ったＧＺＯの膜質なども適用可能である。 In addition, the transparent conductive film generally has a characteristic of having a transmittance of about 90% or more in a visible light region and a resistivity of 1 × 10 −4 Ωcm or less like IZO and a-ITO. I have. Generally, in order for the transparent conductive film to be transparent, the number of conduction electrons must be small, and in order to increase the electrical conductivity, the number of conduction electrons must be large. In the case of a transparent conductive film, these two contradictory conditions must be satisfied. In general, sputtering is used as a method for depositing IZO and a-ITO, but it is easier to adjust the deposition conditions than a CVD (Chemical Vapor Deposition) method, and when manufacturing using a large substrate, There is an advantage that it is easy to make the thickness and characteristics of the thin film uniform. When the sputtering method is used, there are two methods using an oxide target or an alloy target. However, when using an alloy target, the deposition rate is fast, the target life is much longer, and the target can be easily manufactured. It has the advantage that it can be reused and reused, but has the disadvantage of exhibiting property changes that are sensitive to process variables. When an oxide target is used, the stoichiometry of the thin film can be controlled with reproducibility, but the deposition rate is lower than that of an alloy target, and a physical crack may occur in the target during the deposition. However, there is a disadvantage that an arc is generated in the target. When the indium-based oxide is deposited by sputtering, it reacts with O 2 and has a form of In 2 O 3. In order to improve electrical conductivity, Ga, Ge, Si, Ti, Sb, Zr, Sn, Zn and the like are used. In the present invention, ITO means a transparent conductive film in which In 2 O 3 and SnO 2 are mixed at an appropriate ratio, but is not limited thereto. For example, a film quality of GZO made using only Ga and Zn used as a dopant is also applicable.
さらに、前記多層膜は、透明導電膜／銀、透明導電膜／銀合金、透明導電膜／銀／透明導電膜、または透明導電膜／銀合金／透明導電膜で形成された多層膜であってもよい。 Further, the multilayer film is a multilayer film formed of transparent conductive film / silver, transparent conductive film / silver alloy, transparent conductive film / silver / transparent conductive film, or transparent conductive film / silver alloy / transparent conductive film. Is also good.
また、本発明は、本発明の銀エッチング液組成物でエッチングされた配線を提供することができる。 Further, the present invention can provide a wiring etched with the silver etching solution composition of the present invention.
より詳細には、前記配線は、タッチスクリーンパネル（Ｔｏｕｃｈ ｓｃｒｅｅｎ ｐａｎｅｌ、ＴＳＰ）において、主にＸ、Ｙ座標にセンシングされた信号を読み込むトレース（Ｔｒａｃｅ）配線またはフレキシブル用銀ナノワイヤ配線であってもよい。 More specifically, the wiring may be a trace (Trace) wiring or a silver nanowire wiring for flexible, which mainly reads signals sensed at X and Y coordinates in a touch screen panel (Touch screen panel, TSP). .
また、前記配線は、銀（Ａｇ）または銀合金からなる単一膜、または前記単一膜と透明導電膜とから構成される多層膜である。 Further, the wiring is a single film made of silver (Ag) or a silver alloy, or a multilayer film composed of the single film and a transparent conductive film.
前記銀合金は、銀を主成分とし、Ｉｎ、Ｐ、Ｎｄ、Ｃｕ、Ｐｄ、Ｎｂ、Ｎｉ、Ｍｏ、Ｎｉ、Ｃｒ、Ｍｇ、Ｗ、およびＴｉなどの他の金属を含む合金の形態と、銀の窒化物、ケイ化物、炭化物、および酸化物の形態などと多様であり得るが、これらに限定されるものではない。 The silver alloy has a form of an alloy containing silver as a main component and other metals such as In, P, Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W, and Ti; But may be, but not limited to, forms of nitride, silicide, carbide, and oxide.
また、前記透明導電膜は、一般的に、ＩＺＯとａ−ＩＴＯのように、可視光領域で透過率が約９０％以上であり、抵抗率が１×１０−４Ωｃｍ以下の特性を持っている。透明導電膜が透明であるためには、一般的に伝導電子が少なくなければならず、電気伝導度が大きくなるためには、伝導電子が多くなければならない。透明導電膜の場合、このように相反する２つの条件を満足しなければならない。ＩＺＯとａ−ＩＴＯを蒸着する方法には、一般的にスパッタリング（Ｓｐｕｔｔｅｒｉｎｇ）を用いるが、ＣＶＤ（Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ）方法に比べて蒸着条件を調節しやすく、大型の基板を用いて製造する場合、薄膜の厚さおよび薄膜特性の均一化を図るのに容易であるという利点がある。スパッタリング方法で製造する場合、酸化物ターゲットまたは合金ターゲット（ａｌｌｏｙ ｔａｒｇｅｔ）を使用する２つの方法があるが、合金ターゲットを使用する場合、蒸着速度が速く、ターゲット寿命もはるかに長く、ターゲット製造の容易性および再活用が可能であるという利点があるが、工程変数に敏感な特性変化を示すという欠点がある。酸化物ターゲットを用いると、薄膜の化学量論比を再現性あるように制御することができるが、合金ターゲットに比べて蒸着速度が遅く、蒸着途中にターゲットに物理的な亀裂が生じることがあり、ターゲットにアークが生じるという欠点がある。インジウム−主成分系酸化物をスパッタリングによって蒸着させる場合、Ｏ２と反応してＩｎ２Ｏ３の形態を有するが、電気伝導度を向上させるために、ドーパントとして、Ｇａ、Ｇｅ、Ｓｉ、Ｔｉ、Ｓｂ、Ｚｒ、Ｓｎ、およびＺｎなどを使用する。本発明において、ＩＴＯは、それぞれＩｎ２Ｏ３とＳｎＯ２が適正比率で混合されている透明導電膜を意味するが、これに限定されるものではない。例えば、ドーパントとして使用されるＧａとＺｎのみを用いて作ったＧＺＯの膜質なども適用可能である。 In addition, the transparent conductive film generally has a characteristic of having a transmittance of about 90% or more in a visible light region and a resistivity of 1 × 10 −4 Ωcm or less like IZO and a-ITO. I have. Generally, in order for the transparent conductive film to be transparent, the number of conduction electrons must be small, and in order to increase the electrical conductivity, the number of conduction electrons must be large. In the case of a transparent conductive film, these two contradictory conditions must be satisfied. In general, sputtering is used as a method for depositing IZO and a-ITO, but it is easier to adjust the deposition conditions than a CVD (Chemical Vapor Deposition) method, and when manufacturing using a large substrate, There is an advantage that it is easy to make the thickness and characteristics of the thin film uniform. When the sputtering method is used, there are two methods using an oxide target or an alloy target. However, when using an alloy target, the deposition rate is fast, the target life is much longer, and the target can be easily manufactured. It has the advantage that it can be reused and reused, but has the disadvantage of exhibiting property changes that are sensitive to process variables. When an oxide target is used, the stoichiometry of the thin film can be controlled with reproducibility, but the deposition rate is lower than that of an alloy target, and a physical crack may occur in the target during the deposition. However, there is a disadvantage that an arc is generated in the target. When indium-based oxide is deposited by sputtering, it reacts with O 2 and has a form of In 2 O 3. However, in order to improve electric conductivity, Ga, Ge, Si, Ti, Sb, Zr, Sn, Zn and the like are used. In the present invention, ITO means a transparent conductive film in which In 2 O 3 and SnO 2 are mixed at an appropriate ratio, respectively, but is not limited thereto. For example, a film quality of GZO made using only Ga and Zn used as a dopant is also applicable.
さらに、前記多層膜は、透明導電膜／銀、透明導電膜／銀合金、透明導電膜／銀／透明導電膜、または透明導電膜／銀合金／透明導電膜で形成された多層膜であってもよい。 Further, the multilayer film is a multilayer film formed of transparent conductive film / silver, transparent conductive film / silver alloy, transparent conductive film / silver / transparent conductive film, or transparent conductive film / silver alloy / transparent conductive film. Is also good.
以下、実施例を通じて本発明をより詳細に説明する。しかし、下記の実施例は本発明をより具体的に説明するためのものであって、本発明の範囲が下記の実施例によって限定されるものではない。下記の実施例は、本発明の範囲内で当業者によって適切に修正、変更できる。 Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for describing the present invention more specifically, and the scope of the present invention is not limited by the following examples. The following embodiments can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
＜銀エッチング液組成物の製造＞
実施例１〜９および比較例１〜１０
下記表１に記載の成分を当該含有量で混合して銀エッチング液組成物を製造した。（単位：重量％）
<Production of silver etching solution composition>
Examples 1 to 9 and Comparative Examples 1 to 10
The components shown in Table 1 below were mixed at the above contents to prepare a silver etching solution composition. (Unit: wt%)
ＡＴＺ：アミノテトラゾール
実験例１．銀エッチング液組成物の性能テスト
基板上に有機絶縁膜を蒸着し、その上にＡｇ単一膜を蒸着したものを、ダイヤモンドカッタを用いて３００ｘ３００ｍｍに切断して、試験片を用意した。
Experimental Example 1 Performance test of silver etchant composition An organic insulating film was deposited on a substrate, and a single Ag film was deposited on the organic insulating film. The test piece was cut into 300 x 300 mm using a diamond cutter. did.
前記実施例１〜９および比較例１〜１０の銀エッチング液組成物を用いて、下記のような性能テストを行った。 Using the silver etchant compositions of Examples 1 to 9 and Comparative Examples 1 to 10 , the following performance tests were performed.
１．配線（または反射膜）の片側エッチング距離（Ｓ／Ｅ、Ｓｉｄｅ Ｅｔｃｈ）の測定
噴射式エッチング方式の実験装備（モデル名：ＥＴＣＨＥＲ（ＴＦＴ）、Ｋ．Ｃ．Ｔｅｃｈ社）内に、前記実施例１〜９および比較例１〜１０の銀エッチング液組成物をそれぞれ入れて、温度を４０℃に設定して昇温した後、温度が４０±０．１℃に到達した時、前記試験片のエッチング工程を行った。総エッチング時間は６０秒として実施した。
1. Example 1 Measurement of one-sided etching distance (S / E, Side Etch) of wiring (or reflection film) In experimental equipment (model name: ETCHER (TFT), KC Tech) of the injection type etching method, the first embodiment was used. After the silver etchant compositions of Comparative Examples 1 to 9 and Comparative Examples 1 to 10 were respectively added and the temperature was set to 40 ° C and the temperature was raised, when the temperature reached 40 ± 0.1 ° C, etching of the test piece was performed. The process was performed. The total etching time was 60 seconds.
基板を入れて噴射を始めて６０秒のエッチング時間になると、取り出して、脱イオン水で洗浄した後、熱風乾燥装置を用いて乾燥した。洗浄および乾燥後、基板を切断し、断面を電子走査顕微鏡（ＳＥＭ；モデル名：ＳＵ−８０１０、ＨＩＴＡＣＨＩ社製）を用いて測定した。片側エッチング距離の測定基準としては、フォトレジストの端部分から金属がエッチングされて内側まで入った幅を測定し、下記の基準で評価し、結果を下記表２に示した。
＜片側エッチング距離測定の評価基準＞
優秀：０．５μｍ以下
良好：０．５μｍ超過〜１．０μｍ以下
不良：１．０μｍ超過
When the etching time reached 60 seconds after the substrate was put into the chamber and started spraying, the substrate was taken out, washed with deionized water, and then dried using a hot air drier. After washing and drying, the substrate was cut, and the cross section was measured using an electron scanning microscope (SEM; model name: SU-8010, manufactured by HITACHI). As a measurement standard of the one-sided etching distance, a width of the metal etched from the end portion of the photoresist to the inside was measured, and evaluated according to the following criteria. The results are shown in Table 2 below.
<Evaluation criteria for one-sided etching distance measurement>
Excellent: 0.5 μm or less Good: 0.5 μm or more to 1.0 μm or less Poor: 1.0 μm or more
２．残渣の測定
噴射式エッチング方式の実験装備（モデル名：ＥＴＣＨＥＲ（ＴＦＴ）、Ｋ．Ｃ．Ｔｅｃｈ社）内に、前記実施例１〜９および比較例１〜１０の銀エッチング液組成物をそれぞれ入れて、温度を４０℃に設定して加温した後、温度が４０±０．１℃に到達した時、前記試験片のエッチング工程を行った。総エッチング時間は６０秒として実施した。
2. The silver etching solution compositions of Examples 1 to 9 and Comparative Examples 1 to 10 were respectively placed in experimental equipment (model name: ETCHER (TFT), KC Tech) of a residue measurement jet type etching method. After the temperature was set at 40 ° C. and the temperature reached 40 ± 0.1 ° C., the test piece etching step was performed. The total etching time was 60 seconds.
基板を入れて噴射を始めて６０秒のエッチング時間になると、取り出して、脱イオン水で洗浄した後、熱風乾燥装置を用いて乾燥し、フォトレジスト剥離機（ＰＲ ｓｔｒｉｐｐｅｒ）を用いてフォトレジストを除去した。洗浄および乾燥後、電子走査顕微鏡（ＳＥＭ；モデル名：ＳＵ−８０１０、ＨＩＴＡＣＨＩ社製）を用いて、フォトレジストが覆われていない部分に銀（Ａｇ）がエッチングされずに残っている現象である残渣を測定し、下記の基準で評価して、結果を下記表２に示した。
＜残渣測定の評価基準＞
優秀：残渣無し（図１）
不良：残渣発生（残渣はエッチングが不完全になった現象で、基板の全面に無定形で存在する。図２）
When the etching time reaches 60 seconds after the substrate is put in and sprayed, the substrate is taken out, washed with deionized water, dried using a hot air drier, and the photoresist is removed using a photoresist stripper (PR stripper). did. After washing and drying, silver (Ag) remains without being etched in a portion where the photoresist is not covered by using an electron scanning microscope (SEM; model name: SU-8010, manufactured by HITACHI). The residue was measured and evaluated according to the following criteria. The results are shown in Table 2 below.
<Evaluation criteria for residue measurement>
Excellent: No residue (Fig. 1)
Poor: Residue generation (residue is a phenomenon in which etching is incomplete, and is present in an amorphous state over the entire surface of the substrate; FIG. 2).
３．エッチング速度の測定
噴射式エッチング方式の実験装備（モデル名：ＥＴＣＨＥＲ（ＴＦＴ）、Ｋ．Ｃ．Ｔｅｃｈ社）内に、前記実施例１〜９および比較例１〜１０の銀エッチング液組成物をそれぞれ入れて、温度を４０℃に設定して加温した後、温度が４０±０．１℃に到達した時、前記試験片のエッチング工程を行った。総エッチング時間は６０秒として実施した。
3. Measurement of Etching Rate The silver etching solution compositions of Examples 1 to 9 and Comparative Examples 1 to 10 were placed in experimental equipment (model name: ETCHER (TFT), KC Tech) of a jet etching method, respectively. Then, after the temperature was set to 40 ° C. and heated, when the temperature reached 40 ± 0.1 ° C., the test piece etching step was performed. The total etching time was 60 seconds.
肉眼でエンドポイント検出（Ｅｎｄ Ｐｏｉｎｔ Ｄｅｔｅｃｔｉｏｎ、ＥＰＤ）を測定して、時間に応じた縦方向エッチング速度（Ｅ／Ｒ、Ｅｔｃｈ Ｒａｔｅ）を得た。エッチングを進行させた金属膜の厚さをＥＰＤで割ると、秒（時間）あたりのÅ（厚さ）（Å／ｓｅｃ）のエッチング速度を求めることができ、下記の基準で評価して、結果を下記表２に示した。
＜エッチング速度の評価基準＞
優秀：１００Å／ｓｅｃ以下
良好：１００Å／ｓｅｃ超過〜２００Å／ｓｅｃ以下
不良：２００Å／ｓｅｃ超過
The end point detection (End Point Detection, EPD) was measured with the naked eye to obtain a longitudinal etching rate (E / R, Etch Rate) according to time. When the thickness of the metal film that has undergone the etching is divided by the EPD, an etching rate of Å (thickness) per second (time) (Å / sec) can be obtained. Are shown in Table 2 below.
<Evaluation criteria for etching rate>
Excellent: Less than 100 mm / sec Good: More than 100 mm / sec-Less than 200 mm / sec Poor: More than 200 mm / sec
４．経時安定性の測定
前記実施例１〜９および比較例１〜１０の銀エッチング液組成物を用いてレファレンスエッチング（ｒｅｆｅｒｅｎｃｅ ｅｔｃｈ）テストを行い、残りの銀エッチング液組成物を２５℃で計画された日付（１ヶ月基準）の間保管した。その後、保管された銀エッチング液組成物を用いて、前記エッチング速度テストと同一の条件で再びエッチングを進行させて、レファレンスエッチングテストにおける結果と比較した。評価基準は下記の通りであり、結果を下記表２に示した。
＜経時安定性の評価基準＞
優秀：１ヶ月経過後のエッチングプロファイル優秀
良好：１ヶ月経過後のエッチングプロファイル良好
不良：１ヶ月経過後のエッチングプロファイル良好未満の水準
4. Measurement of aging stability A reference etch test was performed using the silver etchant compositions of Examples 1 to 9 and Comparative Examples 1 to 10 , and the remaining silver etchant compositions were designed at 25 ° C. Stored for a date (1 month basis). Thereafter, using the stored silver etchant composition, the etching was performed again under the same conditions as in the etching rate test, and compared with the results of the reference etching test. The evaluation criteria are as follows, and the results are shown in Table 2 below.
<Evaluation criteria for stability over time>
Excellent: Etching profile after one month has passed Excellent: Good etching profile after one month has passed Bad: Etching profile after one month has passed
５．再吸着の測定
噴射式エッチング方式の実験装備（モデル名：ＥＴＣＨＥＲ（ＴＦＴ）、Ｋ．Ｃ．Ｔｅｃｈ社）内に、前記実施例１〜９および比較例１〜１０の銀エッチング液組成物をそれぞれ入れて、温度を４０℃に設定して加温した後、温度が４０±０．１℃に到達した時、前記試験片のエッチング工程を行った。総エッチング時間は６０秒として実施した。
5. Measurement of re-adsorption The silver etching solution compositions of Examples 1 to 9 and Comparative Examples 1 to 10 were respectively installed in experimental equipment (model name: ETCHER (TFT), KC Tech) of a jet type etching method. Then, after the temperature was set to 40 ° C. and heated, when the temperature reached 40 ± 0.1 ° C., the test piece etching step was performed. The total etching time was 60 seconds.
基板を入れて噴射を始めて６０秒のエッチング時間になると、取り出して、脱イオン水で洗浄した後、熱風乾燥装置を用いて乾燥し、フォトレジスト剥離機（ＰＲ ｓｔｒｉｐｐｅｒ）を用いてフォトレジストを除去した。洗浄および乾燥後、電子走査顕微鏡（ＳＥＭ；モデル名：ＳＵ−８０１０、ＨＩＴＡＣＨＩ社製）を用いて、エッチングが行われた後、主にデータ配線などの異種金属が露出した部分や屈曲現象によって摩擦が発生し得る特定部位にエッチングされた銀（Ａｇ）が吸着している現象を全面観察による分析を行い、下記の基準で評価して、結果を下記表２に示した。
＜再吸着測定の評価基準＞
優秀：再吸着無し（図３）
不良：再吸着発生（銀再吸着は還元による吸着で、前記特定部位で球形に観察される。図４）
When the etching time reaches 60 seconds after the substrate is put in and sprayed, the substrate is taken out, washed with deionized water, dried using a hot air drier, and the photoresist is removed using a photoresist stripper (PR stripper). did. After cleaning and drying, after etching is performed using an electron scanning microscope (SEM; model name: SU-8010, manufactured by HITACHI), friction is mainly caused by a portion where a different metal such as a data wiring is exposed or a bending phenomenon. The phenomenon in which the etched silver (Ag) is adsorbed to the specific site where the occurrence of the odor is observed was analyzed by observing the entire surface and evaluated according to the following criteria. The results are shown in Table 2 below.
<Evaluation criteria for re-adsorption measurement>
Excellent: No re-adsorption (Fig. 3)
Poor: Re-adsorption occurred (Silver re-adsorption is adsorption by reduction and is observed spherically at the specific site. FIG. 4)
６．テーパ角（Ｔａｐｅｒ ａｎｇｌｅ）の測定
噴射式エッチング方式の実験装備（モデル名：ＥＴＣＨＥＲ（ＴＦＴ）、Ｋ．Ｃ．Ｔｅｃｈ社）内に、前記実施例１〜９および比較例１〜１０の銀エッチング液組成物をそれぞれ入れて、温度を４０℃に設定して加温した後、温度が４０±０．１℃に到達した時、前記試験片のエッチング工程を行った。総エッチング時間は６０秒として実施した。
6. Measurement of taper angle (Taper angle) The silver etching solution of Examples 1 to 9 and Comparative Examples 1 to 10 was installed in experimental equipment (model name: ETCHER (TFT), KC Tech) of the etching type etching method. After each of the compositions was placed and heated at a temperature of 40 ° C., when the temperature reached 40 ± 0.1 ° C., the test piece etching step was performed. The total etching time was 60 seconds.
基板を入れて噴射を始めて６０秒のエッチング時間になると、取り出して、脱イオン水で洗浄した後、熱風乾燥装置を用いて乾燥し、フォトレジスト剥離機（ＰＲ ｓｔｒｉｐｐｅｒ）を用いてフォトレジストを除去した。洗浄および乾燥後、電子走査顕微鏡（ＳＥＭ；モデル名：ＳＵ−８０１０、ＨＩＴＡＣＨＩ社製）を用いて、エッチングが行われた基板の分析しようとする配線を垂直に切断した後、配線と下部絶縁膜とのなす内側角度を測定して分析を行い、下記の基準で評価して、結果を下記表２に示した。
＜テーパ角測定の評価基準＞
優秀：テーパ角２０゜以上〜６０゜以下（図５）
良好：テーパ角６０゜超過〜８０゜以下
不良：テーパ角２０゜未満または８０゜超過
When the etching time reaches 60 seconds after the substrate is put in and sprayed, the substrate is taken out, washed with deionized water, dried using a hot air drier, and the photoresist is removed using a photoresist stripper (PR stripper). did. After cleaning and drying, the wiring to be analyzed on the etched substrate is vertically cut using an electron scanning microscope (SEM; model name: SU-8010, manufactured by HITACHI), and then the wiring and the lower insulating film are formed. The inside angle formed by the measurement was measured and analyzed, and evaluated according to the following criteria. The results are shown in Table 2 below.
<Evaluation criteria for taper angle measurement>
Excellent: taper angle 20 ° or more to 60 ° or less (Fig. 5)
Good: taper angle more than 60 ° to 80 ° or less Bad: taper angle less than 20 ° or more than 80 °
前記実験結果を通じて、本発明のエッチング液組成物は、片側エッチング距離、残渣、エッチング速度、経時安定性、および再吸着の有無のすべての面において優れるだけでなく、銀を含む金属膜のエッチング時、エッチング後のテーパ角（ｔａｐｅｒ ａｎｇｌｅ）の形成効果を有することを確認した。
Through the above experimental results, the etching solution composition of the present invention is excellent not only in all aspects of one-sided etching distance, residue, etching rate, stability over time, and presence or absence of re-adsorption, but also when etching a metal film containing silver. It has been confirmed that the film has an effect of forming a taper angle after etching.
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| CN113150786A (en) * | 2021-04-26 | 2021-07-23 | 芯越微电子材料(嘉兴)有限公司 | Silver composite film layer etching agent and preparation method thereof |
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