WO2018154775A1 - Etching liquid and use of same - Google Patents

Etching liquid and use of same Download PDF

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Publication number
WO2018154775A1
WO2018154775A1 PCT/JP2017/007466 JP2017007466W WO2018154775A1 WO 2018154775 A1 WO2018154775 A1 WO 2018154775A1 JP 2017007466 W JP2017007466 W JP 2017007466W WO 2018154775 A1 WO2018154775 A1 WO 2018154775A1
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Prior art keywords
copper
etching
hydrogen
transparent conductive
conductive film
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PCT/JP2017/007466
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French (fr)
Japanese (ja)
Inventor
木内丈司
理 嶋田
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富士技研工業株式会社
菱江化学株式会社
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Application filed by 富士技研工業株式会社, 菱江化学株式会社 filed Critical 富士技研工業株式会社
Priority to CN201780087436.0A priority Critical patent/CN110546741A/en
Priority to PCT/JP2017/007466 priority patent/WO2018154775A1/en
Priority to JP2019500999A priority patent/JP6817655B2/en
Publication of WO2018154775A1 publication Critical patent/WO2018154775A1/en

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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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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

Definitions

  • the present invention relates to a technique for etching a transparent conductive film containing indium oxide used in a liquid crystal display or the like, and more particularly to an etching solution used for etching a transparent conductive film having a pattern made of a copper conductor on the surface and use thereof.
  • Transparent conductive films including ITO (indium-tin oxide) films are widely used in the field of electronic devices such as antistatic films, heat reflective films, transparent electrodes of photoelectric conversion elements and various flat panel displays. Recently, with the spread of portable information terminals, notebook PCs, small TVs, etc., the demand for liquid crystal displays (LCDs) has increased.
  • ITO indium-tin oxide
  • the etching solution (Patent Document 2) already completed by the present applicant is composed of a halogen acid, a halogen metal salt, an oxidizing agent, and a remaining diluted solution, and the corrosion amount of the copper conductor in the currently used etching solution for the ITO film.
  • a halogen acid a halogen acid
  • a halogen metal salt a halogen metal salt
  • an oxidizing agent a remaining diluted solution
  • the corrosion amount of the copper conductor in the currently used etching solution for the ITO film There are few drugs. However, even when etching is performed using this etching solution, dissolution of the copper conductor cannot be ignored, and damage to the high-definition copper circuit pattern is inevitable.
  • Patent Document 3 Patent Document 4
  • the manufacturing process of the transparent electrode pattern is efficient.
  • the resistance value of the feeder circuit increases because the etching of the copper conductor in the upper layer of the ITO film proceeds excessively.
  • Patent Document 5 Although a method of using different etching solutions for the etching of the copper film and the etching of the transparent conductor layer has been proposed (Patent Document 5), no detailed examination has been made on the composition of each etching solution here. It cannot be said that it has reached the practical level.
  • JP2015-60937A Japanese Patent No. 4897148 JP 2011-114194 A JP2013-89731A JP 2014-52737 A JP 2017-10996 A JP 2002-241968 A
  • the present invention has been made in view of the above points, and the problem thereof is to selectively use an ITO circuit while maintaining a high etching rate for a crystalline transparent conductive film and without corroding a conductor containing copper as a main component. It is to realize the technique of etching.
  • Another object of the present invention is to provide a transparent conductive film etching method capable of etching only an ITO conductor while suppressing dissolution of a copper conductor.
  • a further object of the present invention is to obtain an etching solution with little change with time.
  • the present inventors were able to selectively dissolve the transparent conductive film without corroding the conductor mainly composed of copper, and the change with time was suppressed.
  • a new high performance etchant has been completed. That is, the present invention is as follows.
  • the (a) hydrogen halide comprises at least one selected from hydrogen chloride, hydrogen bromide, and hydrogen iodide
  • the metal halide (b) is composed of one or more selected from halides of Group 1, 2, and 13 elements of the periodic table
  • the (c) copper dissolution inhibitor comprises one or more selected from hydroxylamine and a salt thereof
  • the (d) diluent is composed of water and / or an organic solvent, and may optionally contain phosphoric acids
  • the (e) oxidizing agent comprises one or more selected from alkali metal and / or alkaline earth metal chlorates, nitrates or nitrites, perchloric acid, nitric acid, hydrogen peroxide, organic peroxides, Used for etching a transparent conductive film having a conductor pattern
  • a transparent conductive film having a conductor pattern mainly composed of copper on its surface containing (a) hydrogen halide, (b) metal halide, (c) copper dissolution inhibitor, (d) diluent, and optionally ( e) A method for etching a transparent conductive film having a conductive pattern mainly composed of copper on the surface, the method comprising a step of contacting an etchant that may contain an oxidizing agent,
  • the (a) hydrogen halide comprises at least one selected from hydrogen chloride, hydrogen bromide, and hydrogen iodide
  • the metal halide (b) is composed of one or more selected from halides of Group 1, 2, and 13 elements of the periodic table
  • the (c) copper dissolution inhibitor comprises one or more selected from hydroxylamine and a salt thereof
  • the (d) diluent is composed of water and / or an organic solvent, and may optionally contain phosphoric acids
  • the (e) oxidizing agent comprises one or more selected from alkali metal and
  • Step 1 A step of forming a transparent conductive film on the substrate,
  • Step 2 A step of forming a conductor film containing copper as a main component on the transparent conductive film,
  • Step 3 A step of etching the conductor film containing copper as a main component to form a conductor pattern containing copper as a main component on the transparent conductive film,
  • Step 4 A transparent conductive film having a conductor pattern mainly composed of copper obtained in Step 3 on its surface is obtained by (a) hydrogen halide, (b) metal halide, (c) copper dissolution inhibitor, ( d) a step of forming a transparent electrode pattern by etching a transparent conductive film by contacting with an etchant containing a diluent and optionally (e) an oxidizing agent;
  • a method for forming a transparent electrode pattern having a copper-based conductor pattern on the surface In step 4 above,
  • the (a) hydrogen halide comprises at least one selected from hydrogen chloride,
  • a copper dissolution inhibitor is newly added to an etching solution in which the main component comprising the components (a) and (b) and the optional component (d) are dissolved in the diluent (d).
  • the transparent conductive film can be etched precisely corresponding to the resist pattern without corroding the copper conductor pattern adjacent thereto. Using such an etching method, the copper conductor and the transparent electrode can be patterned with higher definition.
  • the transparent conductive film which has the conductor pattern which has copper as a main component on the surface just before an etching is represented typically.
  • the transparent electrode which uses the etching liquid of this invention and which has the conductor pattern which has copper as a main component on the surface is represented typically.
  • the resist pattern has already been removed.
  • the transparent electrode which uses the etching liquid for a comparison which does not contain a copper dissolution inhibitor and which has the conductor pattern which has copper as a main component on the surface is represented typically.
  • the resist pattern has already been removed.
  • the etching solution of the present invention contains (a) hydrogen halide, (b) metal halide, (c) copper dissolution inhibitor, (d) diluent, and may optionally contain (e) an oxidizing agent.
  • the hydrogen halide is composed of one or more selected from hydrogen chloride, hydrogen bromide, and hydrogen iodide. Of these, hydrogen chloride (hydrochloric acid) is preferred.
  • hydrogen chloride hydrogen chloride (hydrochloric acid) is preferred.
  • Such (a) hydrogen halide is used in the form dissolved in (d) diluent, preferably in the form of an aqueous solution.
  • concentration of (a) hydrogen halide in the etching solution of the present invention is appropriately adjusted according to the desired etching rate, but is generally 0.1 mol% to 7 mol%, preferably 1.0 mol%. It is in the range of ⁇ 5.0 mol%.
  • the metal halide is composed of one or more selected from halides of Group 1, 2 and 13 elements of the periodic table.
  • metal halide is generally one or more selected from chloride, bromide and iodide of sodium, potassium, magnesium, calcium and aluminum, and the element period in that the etching rate can be increased.
  • Chlorides of Group 2 elements (alkaline earth metals) in the table are preferred, and calcium chloride is particularly preferred.
  • Calcium chloride and other metal halides can be used in combination.
  • a readily available hydrate can be used as calcium chloride.
  • metal halide is used in the form dissolved in (d) diluent, preferably in the form of an aqueous solution.
  • the concentration of the (b) metal halide in the etching solution of the present invention is appropriately adjusted according to the desired etching rate, but is generally 0.01 mol% to 6 mol%, preferably 0.1 mol%. It is in the range of ⁇ 5.0 mol%.
  • the copper dissolution inhibitor is composed of one or more selected from hydroxylamine and a salt thereof.
  • Such (c) copper dissolution inhibitor is used in the form dissolved in (d) diluent, preferably in the form of an aqueous solution. If the density
  • hydroxylammonium chloride When using hydroxylammonium chloride as a copper dissolution inhibitor, generally a 20% by weight aqueous solution of hydroxylammonium chloride is prepared on a weight basis, and (a) hydrogen halide, (b) halogenated. 1 ml or more of the above aqueous solution is added per liter of the mother liquor of the etching solution which may contain metal, (d) diluent, and (e) oxidant, and preferably 1 ml to 20 ml in consideration of cost.
  • the (d) diluent is composed of water and / or an organic solvent, and may optionally contain phosphoric acids.
  • This (d) diluent functions as a solvent for the (a) hydrogen halide, (b) metal halide, and (c) copper dissolution inhibitor contained in the etching solution of the present invention. It also functions as a solvent for the optional component (e) oxidizing agent.
  • ion-exchanged water or distilled water is usually used.
  • the organic solvent used as a diluent is not limited as long as it is an organic solvent that can dissolve the constituents of the etching solution of the present invention, exhibits a relatively low electrical conductivity, and does not affect the etching process. Can be used.
  • organic solvents examples include methanol, ethanol, isopropanol, 1-propanol, 1-butanol, 2-butanol, t-butanol, 2-methyl-1-propanol, 1-pentanol, 1-hexanol, 1 Alcohols such as heptanol, 4-heptanol, 1-octanol, 1-nonyl alcohol, 1-decanol, 1-dodecanol; diols such as ethylene glycol, 1,2-propanediol, propylene glycol, butanediol, glycerin or the like Triols; Ketones such as acetone, acetylacetone, and methyl ethyl ketone; Nitriles such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile; Acetaldehyde, propionaldehyde Which aldehydes; lower alkylene
  • the diluent (d) of the present invention may be the above-mentioned water or the above-mentioned organic solvent, or may be a mixture of the above-mentioned water and the organic solvent in any quantitative ratio. .
  • Phosphoric acids can also be dissolved in the diluent.
  • the phosphoric acids used here include any of phosphoric acid, phosphorous acid, and hypophosphorous acid.
  • the ionization equilibrium of the aqueous solution constituting the etching solution of the present invention can be adjusted by adding one or more of these phosphoric acids to the diluent.
  • These phosphoric acids are supplementary at appropriate concentrations depending on the characteristics of the material to be etched, such as the transparent electrode film to which the etching solution of the present invention is applied, the substrate in contact with the film, and the metal species including copper in the conductor. Can be blended.
  • a diluent (d) of the present invention typically, water and / or alcohol is used.
  • the (e) oxidizing agent increases the etching rate of the etching solution of the present invention and reduces corrosion of the device material by (a) hydrogen halide and (b) metal halide contained in the etching solution of the present invention. Therefore, it is a component used as necessary.
  • Such (e) oxidizing agent is at least one selected from alkali metal and / or alkaline earth metal chlorates, nitrates or nitrites, perchloric acid, nitric acid, hydrogen peroxide, and organic peroxides.
  • an oxidizing agent When an oxidizing agent is used, its addition amount is not limited as long as it does not exceed the saturation amount, but is preferably 0.01 mol% or more, more preferably 0.01 mol% to 2.0 mol%.
  • the halogen concentration per liter of the etching solution of the present invention is 1 mol to the saturation amount, and 10 wt% to 90 wt% of the total halogen amount contained in the etching solution is the above (b) halogenated It is preferably supplied from metal.
  • the transparent conductive film having the copper-based conductor pattern on the surface is used to dissolve the copper conductor. It can be etched without causing it.
  • the “conductor mainly composed of copper” in the present invention is not limited to the case where the conductor is composed of a single copper, but the conductor is composed of a single copper layer and a composite oxide or alloy layer containing copper. This includes cases where
  • a transparent conductive film having a conductor pattern mainly composed of copper on the surface is typically a film in which a circuit pattern composed of a conductor mainly composed of copper is formed on an ITO (indium-tin oxide) film. is there. Such a circuit pattern is formed in an electrode area connected to the display area. Therefore, a typical example of the transparent conductive film having a conductor pattern mainly composed of copper on the surface thereof in the present invention is a portion having a so-called extraction electrode.
  • a resist pattern corresponding to the pattern of the transparent electrode is formed on this film when the transparent conductive film having a conductor pattern mainly composed of copper on the surface and the etching solution of the present invention are brought into contact with each other.
  • the etching method of the present invention a portion of the transparent conductive film not covered with the resist pattern is etched to form a transparent electrode pattern. Since the etching solution of the present invention does not dissolve copper, in this etching method, only the transparent conductive film is etched while the copper pattern already formed on the transparent conductive film is well preserved. As a result, a high-definition copper pattern and transparent electrode pattern are formed.
  • the method of contact between the etching solution of the present invention and the transparent conductive film having a conductor pattern mainly composed of copper on the surface is in accordance with a conventional method of etching treatment.
  • the etching solution of the present invention heated to 30 ° C. to 70 ° C. is brought into contact with a transparent conductive film having a conductor pattern mainly composed of copper on the surface by dipping or spraying at this temperature.
  • the immersion time in the immersion method, the amount of spray liquid in the spray method, and the like are appropriately set in consideration of the etching rate. At this time, by etching while blowing a gaseous oxidant such as oxygen, chlorine, nitrogen oxide, ozone, etc., corrosion of the device material can be reduced and the life of the device can be extended.
  • a gaseous oxidant such as oxygen, chlorine, nitrogen oxide, ozone, etc.
  • a transparent electrode pattern can be formed by a method including the following steps using the etching method of the present invention.
  • Step 1 This is a step of forming a transparent conductive film on the substrate according to a conventional method.
  • a substrate made of glass, quartz, polyethylene terephthalate (PET), polyethersulfone (PES) or the like used for an LCD (liquid crystal display) or a touch panel is used.
  • a glass substrate or a PET substrate is used.
  • the transparent conductive film include films made of ITO (indium tin oxide), indium oxide, tin oxide, and zinc oxide.
  • an ITO film is preferable, and a crystalline ITO film is particularly preferable.
  • a method for forming a transparent conductive film on a substrate sputtering, film deposition, vacuum deposition using ion assist, CVD (chemical vapor deposition), coating, spin coating, or spraying may be used. it can.
  • the thickness of the transparent conductive film is selected according to the thickness according to the target device, but is generally in the range of 100 to 5000 mm.
  • Step 2 A step of forming a conductor film containing copper as a main component on the transparent conductive film according to a conventional method.
  • a method for forming a conductor film containing copper as a main component there are methods such as sputtering, CVD, and electroplating. Generally, sputtering is used.
  • Step 3 the conductor film mainly composed of copper is etched to form a conductor pattern mainly composed of copper on the transparent conductive film.
  • a resist material is applied on a conductor film containing copper as a main component, and a photomask having a pattern drawn on the surface of the resist material is formed.
  • the resist material is irradiated with energy rays such as electromagnetic waves and electron beams through a photomask. The resist material is developed to form a resist pattern.
  • the etching solution used in step 3 is an etching solution that does not corrode the transparent conductive film.
  • an acidic etchant such as a persulfuric acid-based or hydrogen peroxide-based etchant can be used. After selectively etching the copper, the film is washed.
  • Step 4 the transparent conductive film having a conductor pattern mainly composed of copper obtained in step 3 on the surface is etched using the etching solution of the present invention.
  • step 4 a resist material is applied on the transparent conductive film having a conductor pattern mainly composed of copper obtained in step 3 on its surface, and a photomask having a pattern drawn on the surface of the resist material is formed.
  • the resist material is irradiated with energy rays such as electromagnetic waves and electron beams through the photomask. The resist material is developed to form a resist pattern.
  • the transparent conductive film thus obtained is brought into contact with the etching solution of the present invention as described above, and the conductor pattern already formed on the transparent conductive film is well preserved and is not protected with a resist.
  • the transparent conductive film portion is selectively etched. After selectively etching the ITO film, the film is washed.
  • an ITO film having a copper conductive pattern on the surface is etched in two ways: an etching solution of the present invention and (c) a comparative etching solution not containing a copper dissolution inhibitor. The pattern formation of each of the conductor made of copper and the ITO electrode was compared.
  • dihydrate is used as the calcium chloride shown in Table 1, and the concentration indicates the calcium chloride concentration in the mother liquor.
  • Dihydrate is used as the calcium nitrate shown in Table 1, and the concentration indicates the concentration of calcium nitrate in the mother liquor.
  • Step 1 An ITO film having a thickness of 1500 mm was formed on a PET substrate having a thickness of 0.25 mm by sputtering.
  • Step 2 A copper film having a thickness of 1 ⁇ m was formed on the obtained ITO film by sputtering.
  • Step 3 A resist material was applied on the copper film, and the resist material was exposed and developed through a photomask. Thus, a resist pattern was formed on the copper film.
  • the copper film was etched using a commercially available acid etching solution. Thus, a conductor pattern made of copper was formed on the ITO film.
  • Step 4 A resist material was applied to the ITO film on which the conductor pattern made of copper was formed, and the resist material was exposed and developed through a photomask. Thus, a copper conductive pattern and a resist pattern on the ITO film were formed.
  • the resist pattern was formed with a resist line width of approximately 40 ⁇ m and a resist line interval of approximately 20 ⁇ m.
  • the ITO film having the conductor pattern made of copper thus obtained was immersed in the etching solution of the present invention prepared as follows and a comparative etching solution.
  • an ITO film having a thickness of 1500 mm was provided on a PET substrate having a thickness of 0.25 mm by sputtering, and this film was used as a standard film for determining the immersion time.
  • the standard film was previously immersed in each etching solution shown in Table 1, and the time from the start of immersion until the dissolution of the ITO film was completed was defined as the standard time (T).
  • T standard time
  • the completion of dissolution of the ITO film was confirmed by the fact that the surface resistance value of the standard film measured with a tester showed infinite. It shows that the etching rate of each etching liquid is so large that T is small.
  • An ITO film having a conductor pattern made of copper was immersed in each of the etching solutions shown in Table 1 over a time corresponding to T ⁇ 1.5. During immersion, the temperature of each etching solution was maintained at 30 ° C.
  • Etching was performed in such a sufficient time. After the immersion, the ITO film having a conductor pattern made of copper was washed and dried. Thus, an ITO electrode pattern was formed using an etching method using the etching solution of the present invention and the comparative etching solution.
  • FIG. 1 schematically shows an ITO film having a conductor pattern made of copper on the surface immediately before etching in step 4.
  • the resist line spacing (S1) immediately before etching was measured at four different points, and the average value (S1av) of the four values (S11, S12, S13, S14) was obtained.
  • the resist line width (L1) immediately before etching was measured at four different points, and an average value (L1av) of four values (L11, L12, L13, L14) was obtained.
  • FIG. 2 schematically shows an ITO electrode pattern having a conductor pattern made of copper on the surface, formed using the etching solution of the present invention (Examples 1 to 6).
  • FIG. 3 schematically shows an ITO pattern having a conductive pattern made of copper on the surface, formed using a comparative etching solution (Comparative Example 1).
  • the ITO pattern line width after etching (S2) was measured, and the average value (S2av) of the four values (S21, S22, S23, S24) was determined.
  • the ITO pattern line width (L2) after etching was measured, and the average value (L2av) of the four values (L21, L22, L23, L24) was determined.
  • Table 1 shows values of ⁇ S corresponding to Examples 1, 2, 3, 4, and Comparative Example 1.
  • a smaller ⁇ S absolute value means that the resist pattern line spacing is more faithfully reproduced in the ITO electrode pattern line spacing because corrosion of the copper conductor pattern on the ITO film is suppressed.
  • Table 1 shows values of ⁇ L corresponding to Examples 1, 2, 3, 4 and Comparative Example 1. It means that the smaller the absolute value of ⁇ L, the more faithfully the resist pattern line width is reproduced in the ITO electrode pattern line width by suppressing the corrosion of the copper conductor pattern on the ITO film.
  • the resist pattern is accurately reproduced as an ITO electrode pattern.
  • Such a selective etching effect of the etching solution of the present invention is stable until at least 5 hours have passed since the etching solution was prepared.
  • the etching rate does not decrease compared to the case of Comparative Example 1 in which (c) the copper dissolution inhibitor is not used.
  • Example 7 Example 8, Comparative Example 2
  • An etching solution was manufactured under the conditions shown in Table 1. In Examples 8 and 9, etching was performed 24 hours after the addition of 20% by weight aqueous solution of (c) hydroxyammonium hydrochloride. In Comparative Example 2, the mother liquor 24 hours after preparation was used for etching.
  • Etching was performed under the same conditions as in Example 1 using the etching solutions of Example 8 and Comparative Example 2, and evaluated.
  • the contact method of the etching solution was changed from immersion to spraying, and other conditions were the same as in Example 1, and the ITO film was etched and evaluated. The results are shown in Table 2.
  • the selective etching effect of the etching solution of the present invention is maintained even after 24 hours from the preparation of the etching solution or even when the contact method between the etching solution and the ITO film is changed.
  • Example 9 is an example in which (c) a 20% by weight aqueous solution of hydroxyammonium hydrochloride was added in portions to the etching solution.
  • 2 ml of (c) 20% by weight aqueous solution of hydroxyammonium hydrochloride was added to 1 L of the mother liquor shown in Table 1, and 24 hours later, the same amount of (c) A weight percent aqueous solution was added.
  • the ITO film was etched and evaluated under the same conditions as in Example 1 using the etchant at the time when 72 hours had passed since the first addition of (c) hydroxyammonium hydrochloride. The results are shown in Table 3.
  • Example 10 is also an example in which (c) a 20% by weight aqueous solution of hydroxyammonium hydrochloride was dividedly added to the etching solution.
  • (c) a 20% by weight aqueous solution of hydroxyammonium hydrochloride was dividedly added to the etching solution.
  • 2 ml of (c) 20% by weight aqueous solution of hydroxyammonium hydrochloride was added to 1 L of the mother liquor shown in Table 1, 24 hours and 48 hours later, again with the same amount of (c) as above.
  • a 20 wt% aqueous solution of hydroxyammonium hydrochloride was added.
  • the ITO film was etched and evaluated under the same conditions as in Example 1 using the etchant at the time when 72 hours had passed since the first addition of (c) hydroxyammonium hydrochloride. The results are shown in Table 3.
  • Examples 11 and 12 are examples in which (e) the oxidizing agent was not added.
  • the etching solution of the present invention was prepared by adding 2 ml of (c) 20% by weight aqueous solution of hydroxyammonium hydrochloride to 1 L of the mother liquor shown in Table 4, and the ITO film was etched and evaluated under the same conditions as in Example 1. The results are shown in Table 4.
  • the etching solution of the present invention is epoch-making in that it has both an etching rate and selectivity for an ITO film and has little deterioration with time.
  • a transparent electrode pattern having a copper wiring can be efficiently produced with high accuracy.
  • the present invention can contribute to the manufacture of liquid crystal displays and touch panels that are thinner and require high-definition image display.
  • Substrate 2 ITO film 3
  • Copper conductive pattern 4 Resist pattern 5 ITO electrode pattern

Abstract

[Problem] To provide an etching liquid which selectively dissolves a transparent conductive film without corroding copper. [Solution] An etching liquid which contains (a) hydrogen halide, (b) a metal halide, (c) a copper dissolution inhibitor which is selected from among hydroxylamine and salts thereof and (d) a diluent, while optionally containing (e) an oxidant.

Description

エッチング液とその使用Etching solution and its use
　本発明は、液晶ディスプレイ等に使用されるインジウム酸化物を含む透明導電膜のエッチング技術に関し、特に、銅導体から成るパターンを表面に有する透明導電膜のエッチングに用いるエッチング液とその使用に関する。 The present invention relates to a technique for etching a transparent conductive film containing indium oxide used in a liquid crystal display or the like, and more particularly to an etching solution used for etching a transparent conductive film having a pattern made of a copper conductor on the surface and use thereof.
　ＩＴＯ（インジウム－錫酸化物）膜をはじめとする透明導電膜は、帯電防止膜、熱反射膜、光電変換素子や各種フラットパネルディスプレイの透明電極などの電子デバイス分野に広く用いられている。最近では、携帯用情報端末、ノートＰＣ、小型ＴＶなどの普及とともに、液晶ディスプレイ（ＬＣＤ）での需要が増加している。 Transparent conductive films including ITO (indium-tin oxide) films are widely used in the field of electronic devices such as antistatic films, heat reflective films, transparent electrodes of photoelectric conversion elements and various flat panel displays. Recently, with the spread of portable information terminals, notebook PCs, small TVs, etc., the demand for liquid crystal displays (LCDs) has increased.
　ＩＴＯ膜を使用したセンサーはタッチパネルに多く使用されており、近年その感度、反応性の向上に加え、画面そのものが大型化されているなど改良が急速に進みつつある。このようなＩＴＯ膜に代表される透明導電膜に微細な電極パターンを形成させる方法としては、ウェット法、すなわち、ハロゲンイオンを含有する酸性水溶液から成るエッチング液でマスクされていない透明電極膜部分を除去する方法が用いられている（特許文献１）。 Sensors using ITO films are often used for touch panels, and in recent years, in addition to improvements in sensitivity and responsiveness, improvements are rapidly progressing such as the screen itself becoming larger. As a method of forming a fine electrode pattern on a transparent conductive film typified by such an ITO film, a wet method, that is, a transparent electrode film portion that is not masked with an etching solution made of an acidic aqueous solution containing halogen ions is used. A removal method is used (Patent Document 1).
　そのＩＴＯ膜の回路に給電する回路に使用される金属として、近年、比較的安価で導電性能の良い銅が採用され主流になっている。しかし、従来のエッチング液は金属層に対して酸化作用を有し、銅に対しても腐食作用を呈するので、銅導体から成るパターンを有する透明導電膜のエッチングに、そのままでは適用することができない。 In recent years, copper which is relatively inexpensive and has good conductive performance has been adopted as a metal used in a circuit for supplying power to the ITO film circuit. However, since the conventional etching solution has an oxidizing action on the metal layer and also has a corrosive action on copper, it cannot be applied as it is to etching a transparent conductive film having a pattern made of a copper conductor. .
　本出願人が既に完成したエッチング液（特許文献２）は、ハロゲン酸、ハロゲン金属塩、酸化剤及び残部希釈液から成り、現在使用されているＩＴＯ膜に対するエッチング液の中では銅導体の腐食量が少ない薬剤である。しかしながら、このエッチング液を用いてエッチングを行っても、銅導体の溶解は無視できず、高精細な銅回路パターンへのダメージが避けられない。 The etching solution (Patent Document 2) already completed by the present applicant is composed of a halogen acid, a halogen metal salt, an oxidizing agent, and a remaining diluted solution, and the corrosion amount of the copper conductor in the currently used etching solution for the ITO film. There are few drugs. However, even when etching is performed using this etching solution, dissolution of the copper conductor cannot be ignored, and damage to the high-definition copper circuit pattern is inevitable.
　又、塩化第二鉄、塩酸、酸化剤を含むエッチング液を用いて、銅導体とＩＴＯ膜を一括してエッチングする方法（特許文献３、特許文献４）では、透明電極パターンの製造工程を効率化できるという利点はあるものの、ＩＴＯ膜の上部層の銅導体に対するエッチングが進行し過ぎて、給電回路の抵抗値が上がるという問題が生じている。 Further, in the method of etching the copper conductor and the ITO film at once using an etching solution containing ferric chloride, hydrochloric acid, and an oxidizing agent (Patent Document 3, Patent Document 4), the manufacturing process of the transparent electrode pattern is efficient. However, there is a problem that the resistance value of the feeder circuit increases because the etching of the copper conductor in the upper layer of the ITO film proceeds excessively.
　また、銅膜のエッチングと透明導体層のエッチングとで異なるエッチング液を使い分ける方法が提案されているが（特許文献５）、ここではそれぞれのエッチング液の組成について詳細な検討がなされておらず、実用レベルに達しているとは言えない。 Further, although a method of using different etching solutions for the etching of the copper film and the etching of the transparent conductor layer has been proposed (Patent Document 5), no detailed examination has been made on the composition of each etching solution here. It cannot be said that it has reached the practical level.
　さらに従来より、ＩＴＯ膜のエッチング液については、エッチング速度が経時変化することも問題点の一つとして指摘されている（特許文献６、特許文献７）。 Furthermore, it has been pointed out as a problem that the etching rate of the ITO film etchant changes with time (Patent Documents 6 and 7).
特開２０１５－　６０９３７号公報JP2015-60937A 特許第４８９７１４８号公報Japanese Patent No. 4897148 特開２０１１－１１４１９４号公報JP 2011-114194 A 特開２０１３－　８９７３１号公報JP2013-89731A 特開２０１４－　５２７３７号公報JP 2014-52737 A 特開２０１７－　１０９９６号公報JP 2017-10996 A 特開２００２－２４１９６８号公報JP 2002-241968 A
本発明は前記の点に鑑みなされたもので、その課題は結晶系透明導電膜に対する大きいエッチング速度を維持しつつ、かつ、銅を主成分とする導体を腐食することなく、ＩＴＯ回路を選択的にエッチングする技術を実現することである。本発明の他の課題は銅導体の溶解を抑制しつつＩＴＯ導体のみをエッチングすることができる透明導電膜のエッチング方法を提供することにある。またさらに本発明は経時変化の少ないエッチング液を得ることも目的とする。 The present invention has been made in view of the above points, and the problem thereof is to selectively use an ITO circuit while maintaining a high etching rate for a crystalline transparent conductive film and without corroding a conductor containing copper as a main component. It is to realize the technique of etching. Another object of the present invention is to provide a transparent conductive film etching method capable of etching only an ITO conductor while suppressing dissolution of a copper conductor. A further object of the present invention is to obtain an etching solution with little change with time.
　本発明者らは、前記の課題を解決するために努力した結果、銅を主成分とする導体を腐食せず、透明導電膜を選択的に溶解することができ、しかも経時変化が抑えられた、新規で高性能のエッチング液を完成するに至った。すなわち本発明は以下のものである。 As a result of efforts made to solve the above-mentioned problems, the present inventors were able to selectively dissolve the transparent conductive film without corroding the conductor mainly composed of copper, and the change with time was suppressed. A new high performance etchant has been completed. That is, the present invention is as follows.
　（１）
（ａ）ハロゲン化水素、（ｂ）ハロゲン化金属、（ｃ）銅溶解抑制剤、（ｄ）希釈剤を含み、任意に（ｅ）酸化剤を含んでもよく、
上記（ａ）ハロゲン化水素は、塩化水素、臭化水素、ヨウ化水素から選ばれる１以上からなり、
上記（ｂ）ハロゲン化金属は、元素周期表の第１、２、１３族元素のハロゲン化物から選ばれる１以上からなり、
上記（ｃ）銅溶解抑制剤は、ヒドロキシルアミンとその塩から選ばれる１以上からなり、
上記（ｄ）希釈剤は、水及び／又は有機溶媒からなり、任意にリン酸類を含んでもよく、
上記（ｅ）酸化剤は、アルカリ金属及び／又はアルカリ土類金属の塩素酸塩、硝酸塩あるいは亜硝酸塩、過塩素酸、硝酸、過酸化水素、有機過酸化物から選ばれる１以上からなる、
銅を主成分とする導体パターンを表面に有する透明導電膜のエッチングに用いる、
エッチング液。 (1)
(A) a hydrogen halide, (b) a metal halide, (c) a copper dissolution inhibitor, (d) a diluent, optionally (e) an oxidant,
The (a) hydrogen halide comprises at least one selected from hydrogen chloride, hydrogen bromide, and hydrogen iodide,
The metal halide (b) is composed of one or more selected from halides of Group 1, 2, and 13 elements of the periodic table,
The (c) copper dissolution inhibitor comprises one or more selected from hydroxylamine and a salt thereof,
The (d) diluent is composed of water and / or an organic solvent, and may optionally contain phosphoric acids,
The (e) oxidizing agent comprises one or more selected from alkali metal and / or alkaline earth metal chlorates, nitrates or nitrites, perchloric acid, nitric acid, hydrogen peroxide, organic peroxides,
Used for etching a transparent conductive film having a conductor pattern mainly composed of copper on the surface,
Etching solution.
　（２）
銅を主成分とする導体パターンを表面に有する透明導電膜を、（ａ）ハロゲン化水素、（ｂ）ハロゲン化金属、（ｃ）銅溶解抑制剤、（ｄ）希釈剤を含み、任意に（ｅ）酸化剤を含んでよいエッチング液に接触させる工程を含む、銅を主成分とする導体パターンを表面に有する透明導電膜のエッチング方法であって、
上記（ａ）ハロゲン化水素は、塩化水素、臭化水素、ヨウ化水素から選ばれる１以上からなり、
上記（ｂ）ハロゲン化金属は、元素周期表の第１、２、１３族元素のハロゲン化物から選ばれる１以上からなり、
上記（ｃ）銅溶解抑制剤は、ヒドロキシルアミンとその塩から選ばれる１以上からなり、
上記（ｄ）希釈剤は、水及び／又は有機溶媒からなり、任意にリン酸類を含んでもよく、
上記（ｅ）酸化剤は、アルカリ金属及び／又はアルカリ土類金属の塩素酸塩、硝酸塩あるいは亜硝酸塩、過塩素酸、硝酸、過酸化水素、有機過酸化物から選ばれる１以上からなる、
銅を主成分とする導体パターンを表面に有する透明導電膜のエッチング方法。 (2)
A transparent conductive film having a conductor pattern mainly composed of copper on its surface, containing (a) hydrogen halide, (b) metal halide, (c) copper dissolution inhibitor, (d) diluent, and optionally ( e) A method for etching a transparent conductive film having a conductive pattern mainly composed of copper on the surface, the method comprising a step of contacting an etchant that may contain an oxidizing agent,
The (a) hydrogen halide comprises at least one selected from hydrogen chloride, hydrogen bromide, and hydrogen iodide,
The metal halide (b) is composed of one or more selected from halides of Group 1, 2, and 13 elements of the periodic table,
The (c) copper dissolution inhibitor comprises one or more selected from hydroxylamine and a salt thereof,
The (d) diluent is composed of water and / or an organic solvent, and may optionally contain phosphoric acids,
The (e) oxidizing agent comprises one or more selected from alkali metal and / or alkaline earth metal chlorates, nitrates or nitrites, perchloric acid, nitric acid, hydrogen peroxide, organic peroxides,
A method for etching a transparent conductive film having a conductor pattern mainly composed of copper on a surface thereof.
　（３）
以下の工程１～４；
（工程１）基板上に透明導電膜を形成する工程、
（工程２）上記透明導電膜上に銅を主成分とする導体膜を形成する工程、
（工程３）上記銅を主成分とする導体膜をエッチングし、透明導電膜上に銅を主成分とする導体パターンを形成する工程、
（工程４）工程３で得られた銅を主成分とする導体パターンを表面に有する透明導電膜を、（ａ）ハロゲン化水素、（ｂ）ハロゲン化金属、（ｃ）銅溶解抑制剤、（ｄ）希釈剤を含み、任意に（ｅ）酸化剤を含んでよいエッチング液に接触させて、透明導電膜をエッチングし、透明電極パターンを形成する工程、
を有する、銅を主成分とする導体パターンを表面に有する透明電極パターンの形成方法であって、
上記工程４において、
上記（ａ）ハロゲン化水素は、塩化水素、臭化水素、ヨウ化水素から選ばれる１以上からなり、
上記（ｂ）ハロゲン化金属は、元素周期表の第１、２、１３族元素のハロゲン化物から選ばれる１以上からなり、
上記（ｃ）銅溶解抑制剤は、ヒドロキシルアミンとその塩から選ばれる１以上からなり、
上記（ｄ）希釈剤は、水及び／又は有機溶媒からなり、任意にリン酸類を含んでもよく、
上記（ｅ）酸化剤は、アルカリ金属及び／又はアルカリ土類金属の塩素酸塩、硝酸塩あるいは亜硝酸塩、過塩素酸、硝酸、過酸化水素、有機過酸化物から選ばれる１以上からなる、
銅を主成分とする導体パターンを表面に有する透明電極パターンの形成方法。 (3)
The following steps 1 to 4;
(Step 1) A step of forming a transparent conductive film on the substrate,
(Step 2) A step of forming a conductor film containing copper as a main component on the transparent conductive film,
(Step 3) A step of etching the conductor film containing copper as a main component to form a conductor pattern containing copper as a main component on the transparent conductive film,
(Step 4) A transparent conductive film having a conductor pattern mainly composed of copper obtained in Step 3 on its surface is obtained by (a) hydrogen halide, (b) metal halide, (c) copper dissolution inhibitor, ( d) a step of forming a transparent electrode pattern by etching a transparent conductive film by contacting with an etchant containing a diluent and optionally (e) an oxidizing agent;
A method for forming a transparent electrode pattern having a copper-based conductor pattern on the surface,
In step 4 above,
The (a) hydrogen halide comprises at least one selected from hydrogen chloride, hydrogen bromide, and hydrogen iodide,
The metal halide (b) is composed of one or more selected from halides of Group 1, 2, and 13 elements of the periodic table,
The (c) copper dissolution inhibitor comprises one or more selected from hydroxylamine and a salt thereof,
The (d) diluent is composed of water and / or an organic solvent, and may optionally contain phosphoric acids,
The (e) oxidizing agent comprises one or more selected from alkali metal and / or alkaline earth metal chlorates, nitrates or nitrites, perchloric acid, nitric acid, hydrogen peroxide, organic peroxides,
A method for forming a transparent electrode pattern having a conductor pattern mainly composed of copper on the surface.
　本発明は、上記成分（ａ），（ｂ）からなる主成分と任意成分（ｄ）とが希釈剤（ｄ）に溶解したエッチング液に、新たに（ｃ）銅溶解抑制剤を添加することにより、エッチング液の金属銅に対する腐食作用を著しく低減することに成功した。 In the present invention, (c) a copper dissolution inhibitor is newly added to an etching solution in which the main component comprising the components (a) and (b) and the optional component (d) are dissolved in the diluent (d). Thus, the corrosive action of the etchant on metallic copper was successfully reduced.
　本発明のエッチング液を用いれば、透明導電膜を、これに隣接する銅導体パターンを腐食することなく、レジストパターンに精細に対応してエッチングすることができる。このようなエッチング方法を用いて、銅導体と透明電極とをより高精細にパターニングすることができる。 If the etching solution of the present invention is used, the transparent conductive film can be etched precisely corresponding to the resist pattern without corroding the copper conductor pattern adjacent thereto. Using such an etching method, the copper conductor and the transparent electrode can be patterned with higher definition.
エッチング直前の、銅を主成分とする導体パターンを表面に有する透明導電膜を、模式的に表す。The transparent conductive film which has the conductor pattern which has copper as a main component on the surface just before an etching is represented typically. 本発明のエッチング液を用いて形成された、銅を主成分とする導体パターンを表面に有する透明電極を、模式的に表す。ここではレジストパターンはすでに除去されている。The transparent electrode which uses the etching liquid of this invention and which has the conductor pattern which has copper as a main component on the surface is represented typically. Here, the resist pattern has already been removed. （ｃ）銅溶解抑制剤を含まない比較用のエッチング液を用いて形成された、銅を主成分とする導体パターンを表面に有する透明電極を、模式的に表す。ここではレジストパターンはすでに除去されている。(C) The transparent electrode which uses the etching liquid for a comparison which does not contain a copper dissolution inhibitor and which has the conductor pattern which has copper as a main component on the surface is represented typically. Here, the resist pattern has already been removed.
　（エッチング液）
　本発明のエッチング液は、（ａ）ハロゲン化水素、（ｂ）ハロゲン化金属、（ｃ）銅溶解抑制剤、（ｄ）希釈剤を含み、任意に（ｅ）酸化剤を含んでもよい。 (Etching solution)
The etching solution of the present invention contains (a) hydrogen halide, (b) metal halide, (c) copper dissolution inhibitor, (d) diluent, and may optionally contain (e) an oxidizing agent.
　上記（ａ）ハロゲン化水素は、塩化水素、臭化水素、ヨウ化水素から選ばれる１以上からなる。このうち塩化水素（塩酸）が好ましい。このような（ａ）ハロゲン化水素は（ｄ）希釈剤に溶解した形で、好ましくは水溶液の形で用いられる。本発明のエッチング液中の（ａ）ハロゲン化水素の濃度は所望のエッチング速度に応じて適宜調節されるが、一般的には０．１モル％～７モル％、好ましくは１．０モル％～５．０モル％の範囲にある。 (A) The hydrogen halide is composed of one or more selected from hydrogen chloride, hydrogen bromide, and hydrogen iodide. Of these, hydrogen chloride (hydrochloric acid) is preferred. Such (a) hydrogen halide is used in the form dissolved in (d) diluent, preferably in the form of an aqueous solution. The concentration of (a) hydrogen halide in the etching solution of the present invention is appropriately adjusted according to the desired etching rate, but is generally 0.1 mol% to 7 mol%, preferably 1.0 mol%. It is in the range of ˜5.0 mol%.
　上記（ｂ）ハロゲン化金属は、元素周期表の第１、２、１３族元素のハロゲン化物から選ばれる１以上からなる。このような（ｂ）ハロゲン化金属としては、一般的にはナトリウム、カリウム、マグネシウム、カルシウム、アルミニウムの塩化物、臭化物、ヨウ化物から選ばれる１以上であり、エッチング速度を上昇できる点で元素周期表の第２族元素（アルカリ土類金属）の塩化物が好ましく、塩化カルシウムが特に好ましい。塩化カルシウムと他のハロゲン化金属とを併用することもできる。塩化カルシウムとしては入手が容易な水和物を使用することができる。このような（ｂ）ハロゲン化金属は（ｄ）希釈剤に溶解した形で、好ましくは水溶液の形で用いられる。本発明のエッチング液中の（ｂ）ハロゲン化金属の濃度は所望のエッチング速度に応じて適宜調節されるが、一般的には０．０１モル％～６モル％、好ましくは０．１モル％～５．０モル％の範囲にある。 (B) The metal halide is composed of one or more selected from halides of Group 1, 2 and 13 elements of the periodic table. Such (b) metal halide is generally one or more selected from chloride, bromide and iodide of sodium, potassium, magnesium, calcium and aluminum, and the element period in that the etching rate can be increased. Chlorides of Group 2 elements (alkaline earth metals) in the table are preferred, and calcium chloride is particularly preferred. Calcium chloride and other metal halides can be used in combination. A readily available hydrate can be used as calcium chloride. Such (b) metal halide is used in the form dissolved in (d) diluent, preferably in the form of an aqueous solution. The concentration of the (b) metal halide in the etching solution of the present invention is appropriately adjusted according to the desired etching rate, but is generally 0.01 mol% to 6 mol%, preferably 0.1 mol%. It is in the range of ˜5.0 mol%.
　上記（ｃ）銅溶解抑制剤は、ヒドロキシルアミンとその塩から選ばれる１以上からなる。ヒドロキシルアミンの塩としては、塩化ヒドロキシルアンモニウム、硝酸ヒドロキシルアンモニウム、硫酸ヒドロキシルアンモニウムを用いることができ、中でも塩化ヒドロキシルアンモニウムが好ましい。このような（ｃ）銅溶解抑制剤は（ｄ）希釈剤に溶解した形で、好ましくは水溶液の形で用いられる。本発明のエッチング液中の（ｃ）銅溶解抑制剤の濃度は本発明のエッチング液の銅溶解性を抑制する効果を与えられる濃度以上であれば制限はない。 (C) The copper dissolution inhibitor is composed of one or more selected from hydroxylamine and a salt thereof. As the salt of hydroxylamine, hydroxylammonium chloride, hydroxylammonium nitrate, and hydroxylammonium sulfate can be used, and among them, hydroxylammonium chloride is preferable. Such (c) copper dissolution inhibitor is used in the form dissolved in (d) diluent, preferably in the form of an aqueous solution. If the density | concentration of (c) copper dissolution inhibitor in the etching liquid of this invention is more than the density | concentration which can give the effect which suppresses the copper solubility of the etching liquid of this invention, there will be no restriction | limiting.
　（ｃ）銅溶解抑制剤として塩化ヒドロキシルアンモニウムを用いる場合には、一般的には、重量基準で塩化ヒドロキシルアンモニウムの２０重量％の水溶液を調整し、（ａ）ハロゲン化水素、（ｂ）ハロゲン化金属、（ｄ）希釈剤、任意に（ｅ）酸化剤を含んでよいエッチング液の母液１Ｌ当たり上記水溶液を１ｍｌ以上、コストを考慮して好ましくは１ｍｌ～２０ｍｌ添加する。 (C) When using hydroxylammonium chloride as a copper dissolution inhibitor, generally a 20% by weight aqueous solution of hydroxylammonium chloride is prepared on a weight basis, and (a) hydrogen halide, (b) halogenated. 1 ml or more of the above aqueous solution is added per liter of the mother liquor of the etching solution which may contain metal, (d) diluent, and (e) oxidant, and preferably 1 ml to 20 ml in consideration of cost.
　上記（ｄ）希釈剤は、水及び／又は有機溶媒からなり、任意にリン酸類を含んでもよい。この（ｄ）希釈剤は、本発明のエッチング液に含まれる（ａ）ハロゲン化水素、（ｂ）ハロゲン化金属、（ｃ）銅溶解抑制剤の溶媒として機能し、また本発明のエッチング液の任意成分である（ｅ）酸化剤の溶媒としても機能する。 The (d) diluent is composed of water and / or an organic solvent, and may optionally contain phosphoric acids. This (d) diluent functions as a solvent for the (a) hydrogen halide, (b) metal halide, and (c) copper dissolution inhibitor contained in the etching solution of the present invention. It also functions as a solvent for the optional component (e) oxidizing agent.
　（ｄ）希釈剤として用いられる水としては、通常イオン交換水または蒸留水が用いられる。（ｄ）希釈剤として用いられる有機溶媒としては、本発明のエッチング液の構成成分を溶解することができ、比較的低い電気伝導度を示し、エッチング処理に影響のない有機溶媒であれば制限なく使用することができる。このような有機溶媒としては、例えば、メタノール、エタノール、イソプロパノール、１－プロパノール、１－ブタノール、２－ブタノール、ｔ－ブタノール、２－メチル－１－プロパノール、１－ペンタノール、１－ヘキサノール、１－ヘプタノール、４－ヘプタノール、１－オクタノール、１－ノニルアルコール、１－デカノール、１－ドデカノールなどのアルコール類；エチレングリコール、１，２－プロパンジオール、プロピレングリコール、ブタンジオール類、グリセリンなどのジオールまたはトリオール類；アセトン、アセチルアセトン、メチルエチルケトン等のケトン類；アセトニトリル、プロピオニトリル、ブチロニトリル、イソブチロニトリル、ベンゾニトリル等のニトリル類；アセトアルデヒド、プロピオンアルデヒドなどのアルデヒド類；エチレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテルなどの低級アルキレングリコールモノアルキルエーテル；テトラヒドロフラン、ジオキサン等のエーテル類、トリフルオロエタノール、ペンタフルオロプロパノール、2,2,3,3－テトラフルオロプロパノール等の含フッ素アルコール、スルホラン等の有機溶媒を用いることができる。このような有機溶媒の中で、取扱性が容易である点では、メタノール、エタノール、イソプロパノール、１－プロパノールなどの低級アルコールが好ましい。また、このような有機溶媒として２種以上の混合物も用いることができる。本発明の（ｄ）希釈剤としては、上述の水であっても、また上述の有機溶媒であってもよく、上述の水及び有機溶媒を任意の量比で混合したものであってもよい。 (D) As water used as a diluent, ion-exchanged water or distilled water is usually used. (D) The organic solvent used as a diluent is not limited as long as it is an organic solvent that can dissolve the constituents of the etching solution of the present invention, exhibits a relatively low electrical conductivity, and does not affect the etching process. Can be used. Examples of such organic solvents include methanol, ethanol, isopropanol, 1-propanol, 1-butanol, 2-butanol, t-butanol, 2-methyl-1-propanol, 1-pentanol, 1-hexanol, 1 Alcohols such as heptanol, 4-heptanol, 1-octanol, 1-nonyl alcohol, 1-decanol, 1-dodecanol; diols such as ethylene glycol, 1,2-propanediol, propylene glycol, butanediol, glycerin or the like Triols; Ketones such as acetone, acetylacetone, and methyl ethyl ketone; Nitriles such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile; Acetaldehyde, propionaldehyde Which aldehydes; lower alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and propylene glycol monoethyl ether; ethers such as tetrahydrofuran and dioxane, trifluoroethanol, pentafluoropropanol, 2,2,3,3-tetrafluoropropanol Organic solvents such as fluorine-containing alcohols such as sulfolane and sulfolane can be used. Of these organic solvents, lower alcohols such as methanol, ethanol, isopropanol, and 1-propanol are preferable because they are easy to handle. In addition, a mixture of two or more kinds can be used as such an organic solvent. The diluent (d) of the present invention may be the above-mentioned water or the above-mentioned organic solvent, or may be a mixture of the above-mentioned water and the organic solvent in any quantitative ratio. .
　（ｄ）希釈剤にはさらに、リン酸類を溶解させることもできる。ここで用いるリン酸類にはリン酸、亜リン酸、次亜リン酸のいずれもが包含される。（ｄ）希釈剤にこれらリン酸類の１以上を添加することによって本発明のエッチング液を構成する水溶液の電離平衡を調節することができる。これらリン酸類は、本発明のエッチング液が適用される透明電極膜、これに接する基板、導体における銅をはじめとする金属種などの、被エッチング材料の特性に応じて、適当な濃度で補助的に配合することができる。 (D) Phosphoric acids can also be dissolved in the diluent. The phosphoric acids used here include any of phosphoric acid, phosphorous acid, and hypophosphorous acid. (D) The ionization equilibrium of the aqueous solution constituting the etching solution of the present invention can be adjusted by adding one or more of these phosphoric acids to the diluent. These phosphoric acids are supplementary at appropriate concentrations depending on the characteristics of the material to be etched, such as the transparent electrode film to which the etching solution of the present invention is applied, the substrate in contact with the film, and the metal species including copper in the conductor. Can be blended.
　このような本発明の（ｄ）希釈剤としては、典型的には、水及び／又はアルコールが用いられる。 As such a diluent (d) of the present invention, typically, water and / or alcohol is used.
　上記（ｅ）酸化剤は、本発明のエッチング液のエッチング速度を上昇させると共に、本発明のエッチング液に含まれる（ａ）ハロゲン化水素及び（ｂ）ハロゲン化金属による装置材料の腐食を低減させるために、必要に応じて使用される成分である。このような（ｅ）酸化剤は、アルカリ金属及び／又はアルカリ土類金属の塩素酸塩、硝酸塩あるいは亜硝酸塩、過塩素酸、硝酸、過酸化水素、有機過酸化物から選ばれる１以上であり、好ましくはナトリウムまたはカルシウムの塩素酸塩、硝酸塩、過酸化水素、有機過酸化物である。（ｅ）酸化剤を用いる場合には、その添加量は飽和量を超えない限り制限はないが、エッチング液全量に対して好ましくは０．０１モル％以上、より好ましくは０．０１モル％～２．０モル％である。 The (e) oxidizing agent increases the etching rate of the etching solution of the present invention and reduces corrosion of the device material by (a) hydrogen halide and (b) metal halide contained in the etching solution of the present invention. Therefore, it is a component used as necessary. Such (e) oxidizing agent is at least one selected from alkali metal and / or alkaline earth metal chlorates, nitrates or nitrites, perchloric acid, nitric acid, hydrogen peroxide, and organic peroxides. Preferably, sodium or calcium chlorate, nitrate, hydrogen peroxide, organic peroxide. (E) When an oxidizing agent is used, its addition amount is not limited as long as it does not exceed the saturation amount, but is preferably 0.01 mol% or more, more preferably 0.01 mol% to 2.0 mol%.
　また、エッチング速度から見て、本発明のエッチング液１Ｌあたりのハロゲン濃度を１モル～飽和量であり、エッチング液に含まれる全ハロゲン量の１０重量％～９０重量％が上記（ｂ）ハロゲン化金属から供給されることが好ましい。 Further, in view of the etching rate, the halogen concentration per liter of the etching solution of the present invention is 1 mol to the saturation amount, and 10 wt% to 90 wt% of the total halogen amount contained in the etching solution is the above (b) halogenated It is preferably supplied from metal.
　（エッチング方法）
　本発明のエッチング液を銅を主成分とする導体パターンを表面に有する透明導電膜と接触させることによって、上記銅を主成分とする導体パターンを表面に有する透明導電膜を、銅導体の溶解を引き起こさずにエッチングすることができる。 (Etching method)
By bringing the etching liquid of the present invention into contact with a transparent conductive film having a copper-based conductor pattern on the surface, the transparent conductive film having the copper-based conductor pattern on the surface is used to dissolve the copper conductor. It can be etched without causing it.
　なお、本発明における「銅を主成分とする導体」は、導体が銅単体から構成される場合だけでなく、導体が銅単体層と銅を含有する複合酸化物あるいは合金の層とで構成される場合も含む。 The “conductor mainly composed of copper” in the present invention is not limited to the case where the conductor is composed of a single copper, but the conductor is composed of a single copper layer and a composite oxide or alloy layer containing copper. This includes cases where
　銅を主成分とする導体パターンを表面に有する透明導電膜は、典型的には、ＩＴＯ（インジウム－錫酸化物）膜上に銅を主成分とする導体からなる回路パターンが形成された膜である。このような回路パターンは表示エリアに接続される電極エリアに形成される。従って本発明における銅を主成分とする導体パターンを表面に有する透明導電膜の典型例は、いわゆる引き出し電極を有する部位である。 A transparent conductive film having a conductor pattern mainly composed of copper on the surface is typically a film in which a circuit pattern composed of a conductor mainly composed of copper is formed on an ITO (indium-tin oxide) film. is there. Such a circuit pattern is formed in an electrode area connected to the display area. Therefore, a typical example of the transparent conductive film having a conductor pattern mainly composed of copper on the surface thereof in the present invention is a portion having a so-called extraction electrode.
　このような銅を主成分とする導体パターンを表面に有する透明導電膜と、本発明のエッチング液との接触時には、この膜上に透明電極のパターンに応じたレジストパターンが形成されている。本発明のエッチング方法により、透明導電膜のレジストパターンで被覆されていない部分がエッチングされ、透明電極パターンが形成される。本発明のエッチング液は銅を溶解することがないため、このエッチング方法では透明導電膜上にすでに形成されている銅パターンが良好に保存された状態で透明導電膜だけがエッチングされる。その結果、高精細な銅パターンと透明電極パターンが形成される。 A resist pattern corresponding to the pattern of the transparent electrode is formed on this film when the transparent conductive film having a conductor pattern mainly composed of copper on the surface and the etching solution of the present invention are brought into contact with each other. According to the etching method of the present invention, a portion of the transparent conductive film not covered with the resist pattern is etched to form a transparent electrode pattern. Since the etching solution of the present invention does not dissolve copper, in this etching method, only the transparent conductive film is etched while the copper pattern already formed on the transparent conductive film is well preserved. As a result, a high-definition copper pattern and transparent electrode pattern are formed.
　本発明のエッチング液と銅を主成分とする導体パターンを表面に有する透明導電膜との接触の方法は、エッチング処理の定法に従う。一般的には、３０℃～７０℃に加温された本発明のエッチング液を、この温度下で浸漬法やスプレー法で銅を主成分とする導体パターンを表面に有する透明導電膜と接触させる。浸漬法における浸漬時間、スプレー法におけるスプレー液量などは、エッチング速度を考慮して適宜設定される。またこの時、酸素、塩素、酸化窒素、オゾンなどの気体状酸化剤を吹き込みながらエッチングすることで装置材料の腐食を軽減し、装置の寿命を延ばすこともできる。 The method of contact between the etching solution of the present invention and the transparent conductive film having a conductor pattern mainly composed of copper on the surface is in accordance with a conventional method of etching treatment. In general, the etching solution of the present invention heated to 30 ° C. to 70 ° C. is brought into contact with a transparent conductive film having a conductor pattern mainly composed of copper on the surface by dipping or spraying at this temperature. . The immersion time in the immersion method, the amount of spray liquid in the spray method, and the like are appropriately set in consideration of the etching rate. At this time, by etching while blowing a gaseous oxidant such as oxygen, chlorine, nitrogen oxide, ozone, etc., corrosion of the device material can be reduced and the life of the device can be extended.
　（透明電極パターンの形成方法）
本発明のエッチング方法を利用した、以下の工程を含む方法によって、透明電極パターンを形成することができる。 (Transparent electrode pattern formation method)
A transparent electrode pattern can be formed by a method including the following steps using the etching method of the present invention.
　（工程１）定法に従い基板上に透明導電膜を形成する工程である。基板としては、ＬＣＤ（液晶ディスプレイ）やタッチパネル等に用いられる、ガラス、石英、ポリエチレンテレフタレート（ＰＥＴ）、ポリエーテルスルフォン（ＰＥＳ）などからなる基板が用いられ、一般的にはガラス基板、ＰＥＴ基板が用いられる。透明導電膜としてはＩＴＯ（酸化インジウム錫）、酸化インジウム、酸化錫、酸化亜鉛からなる膜が挙げられる。本発明の透明導電膜としてはＩＴＯ膜が好ましく、特に結晶タイプのＩＴＯ膜が好ましい。基板上に透明導電膜を形成する方法としては、スパッタリング、フィルム蒸着や、イオンアシスト等を使った真空蒸着、ＣＶＤ（化学的気相法）、塗布、スピンコート、スプレー法のいずれも用いることができる。透明導電膜の厚みは目的のデバイスに応じた厚みによって選択されるが、１００Å～５０００Åの範囲が一般的である。 (Step 1) This is a step of forming a transparent conductive film on the substrate according to a conventional method. As the substrate, a substrate made of glass, quartz, polyethylene terephthalate (PET), polyethersulfone (PES) or the like used for an LCD (liquid crystal display) or a touch panel is used. Generally, a glass substrate or a PET substrate is used. Used. Examples of the transparent conductive film include films made of ITO (indium tin oxide), indium oxide, tin oxide, and zinc oxide. As the transparent conductive film of the present invention, an ITO film is preferable, and a crystalline ITO film is particularly preferable. As a method for forming a transparent conductive film on a substrate, sputtering, film deposition, vacuum deposition using ion assist, CVD (chemical vapor deposition), coating, spin coating, or spraying may be used. it can. The thickness of the transparent conductive film is selected according to the thickness according to the target device, but is generally in the range of 100 to 5000 mm.
　（工程２）定法に従い上記透明導電膜上に銅を主成分とする導体膜を形成する工程である。銅を主成分とする導体膜を形成する方法としてはスパッタリング、ＣＶＤ、電気メッキなどの方法があるが、一般的にはスパッタリングが用いられる。 (Step 2) A step of forming a conductor film containing copper as a main component on the transparent conductive film according to a conventional method. As a method for forming a conductor film containing copper as a main component, there are methods such as sputtering, CVD, and electroplating. Generally, sputtering is used.
　（工程３）上記銅を主成分とする導体膜をエッチングし、透明導電膜上に銅を主成分とする導体パターンを形成する工程である。工程３では、銅を主成分とする導体膜上にレジスト材料を塗布し、レジスト材料の表面にパターンが描かれたフォトマスクを形成する。次に、フォトマスクを通して電磁波や電子線などのエネルギー線をレジスト材料に照射する。レジスト材料を現像してレジストパターンを形成する。 (Step 3) In this step, the conductor film mainly composed of copper is etched to form a conductor pattern mainly composed of copper on the transparent conductive film. In step 3, a resist material is applied on a conductor film containing copper as a main component, and a photomask having a pattern drawn on the surface of the resist material is formed. Next, the resist material is irradiated with energy rays such as electromagnetic waves and electron beams through a photomask. The resist material is developed to form a resist pattern.
　次に、銅を主成分とする導体膜をエッチングする。工程３で用いられるエッチング液は透明導電膜を腐食しないエッチング液である。このようなエッチング液として、過硫酸系あるいは過酸化水素系エッチング液などの酸性エッチング液を使用することができる。銅を選択的にエッチングした後、膜を洗浄する。 Next, the conductor film containing copper as a main component is etched. The etching solution used in step 3 is an etching solution that does not corrode the transparent conductive film. As such an etchant, an acidic etchant such as a persulfuric acid-based or hydrogen peroxide-based etchant can be used. After selectively etching the copper, the film is washed.
　（工程４）工程３で得られた銅を主成分とする導体パターンを表面に有する透明導電膜を、本発明のエッチング液を用いてエッチングする工程である。工程４では、工程３で得られた銅を主成分とする導体パターンを表面に有する透明導電膜上にレジスト材料を塗布し、レジスト材料の表面にパターンが描かれたフォトマスクを形成する。次に、このフォトマスクを通して電磁波や電子線などのエネルギー線をレジスト材料に照射する。レジスト材料を現像してレジストパターンを形成する。こうして得られた透明導電膜を、上述のように本発明のエッチング液と接触させて、透明導電膜上にすでに形成されている導体パターンが良好に保存される状態で、レジストで保護されていない透明導電膜部分を選択的にエッチングする。ＩＴＯ膜を選択的にエッチングした後、膜を洗浄する。 (Step 4) In this step, the transparent conductive film having a conductor pattern mainly composed of copper obtained in step 3 on the surface is etched using the etching solution of the present invention. In step 4, a resist material is applied on the transparent conductive film having a conductor pattern mainly composed of copper obtained in step 3 on its surface, and a photomask having a pattern drawn on the surface of the resist material is formed. Next, the resist material is irradiated with energy rays such as electromagnetic waves and electron beams through the photomask. The resist material is developed to form a resist pattern. The transparent conductive film thus obtained is brought into contact with the etching solution of the present invention as described above, and the conductor pattern already formed on the transparent conductive film is well preserved and is not protected with a resist. The transparent conductive film portion is selectively etched. After selectively etching the ITO film, the film is washed.
　［実施例１～６、比較例１］
　以下のように、銅からなる導体パターンを表面に有するＩＴＯ膜を、本発明のエッチング液と、（ｃ）銅溶解抑制剤を含まない比較用のエッチング液の２通りでエッチングして、エッチング後の、銅からなる導体とＩＴＯ電極のそれぞれのパターン形成を比較した。 [Examples 1 to 6, Comparative Example 1]
After etching, an ITO film having a copper conductive pattern on the surface is etched in two ways: an etching solution of the present invention and (c) a comparative etching solution not containing a copper dissolution inhibitor. The pattern formation of each of the conductor made of copper and the ITO electrode was compared.
　（エッチング液の製造）　
　（ａ）ハロゲン化水素としての塩酸、（ｂ）ハロゲン化金属としての塩化カルシウム、（ｄ）希釈剤としての水、任意に配合できる（ｅ）酸化剤としての硝酸カルシウムを、表１に示す配合で混合し、エッチング液の母液を調製した。表１に示す濃度（モル％）は、（ｄ）水で希釈された上記（ａ），（ｂ），（ｅ）の濃度である。この母液１Ｌあたり表１に示す量の（ｃ）銅溶解抑制剤としての塩酸ヒドロキシアンモニウムの２０重量％水溶液を添加、混合した後、表１に示す一定時間（ｔ）静置したものを本発明のエッチング液（実施例１～６）として用いた。ｔが０の場合は、上記母液に表１に示す（ｃ）銅溶解抑制剤を添加、混合した直後にエッチングに用いたことを示す。 (Manufacture of etchant)
(A) Hydrochloric acid as a hydrogen halide, (b) calcium chloride as a metal halide, (d) water as a diluent, (e) calcium nitrate as an oxidizing agent, which can be optionally blended, as shown in Table 1. To prepare an etching solution mother liquor. The concentrations (mol%) shown in Table 1 are the concentrations of the above (a), (b), and (e) diluted with (d) water. The amount of (c) 20% by weight aqueous solution of hydroxyammonium hydrochloride as a copper dissolution inhibitor in the amount shown in Table 1 per 1 liter of the mother liquor was added and mixed, and then the mixture was allowed to stand for a certain time (t) as shown in Table 1 As an etching solution (Examples 1 to 6). When t is 0, it indicates that (c) the copper dissolution inhibitor shown in Table 1 was added to the mother liquor and was used for etching immediately after mixing.
　これに対して、（ｃ）銅溶解抑制剤を添加しない母液を比較用のエッチング液（比較例１）として用いた。 In contrast, (c) a mother liquor to which no copper dissolution inhibitor was added was used as a comparative etching solution (Comparative Example 1).
　なお、表１に示す塩化カルシウムとして２水和物を使用し、その濃度は母液中の塩化カルシウム濃度を示す。表１に示す硝酸カルシウムとして２水和物を使用し、その濃度は母液中の硝酸カルシウム濃度を示す。 In addition, dihydrate is used as the calcium chloride shown in Table 1, and the concentration indicates the calcium chloride concentration in the mother liquor. Dihydrate is used as the calcium nitrate shown in Table 1, and the concentration indicates the concentration of calcium nitrate in the mother liquor.
　（エッチング及び透明電極パターンの形成）
（工程１）厚み０．２５ｍｍのＰＥＴ基板上に、スパッタリングによって厚みが１５００ÅのＩＴＯ膜を形成した。（工程２）得られたＩＴＯ膜上にスパッタリングによって厚み１μｍの銅膜を形成した。（工程３）銅膜上にレジスト材料を塗布し、フォトマスクを通してレジスト材料を露光、現像した。こうして銅膜上にレジストパターンを形成した。これを、市販の酸性エッチング液を用いて銅膜をエッチングした。こうして銅からなる導体パターンがＩＴＯ膜上に形成された。（工程４）銅からなる導体パターンが形成されたＩＴＯ膜にレジスト材料を塗布し、フォトマスクを通してレジスト材料を露光、現像した。こうして銅からなる導体パターン及びＩＴＯ膜の上のレジストパターンを形成した。レジストパターンは、概ね４０μｍのレジスト線幅、概ね２０μｍのレジスト線間隔で形成された。 (Etching and formation of transparent electrode pattern)
(Step 1) An ITO film having a thickness of 1500 mm was formed on a PET substrate having a thickness of 0.25 mm by sputtering. (Step 2) A copper film having a thickness of 1 μm was formed on the obtained ITO film by sputtering. (Step 3) A resist material was applied on the copper film, and the resist material was exposed and developed through a photomask. Thus, a resist pattern was formed on the copper film. The copper film was etched using a commercially available acid etching solution. Thus, a conductor pattern made of copper was formed on the ITO film. (Step 4) A resist material was applied to the ITO film on which the conductor pattern made of copper was formed, and the resist material was exposed and developed through a photomask. Thus, a copper conductive pattern and a resist pattern on the ITO film were formed. The resist pattern was formed with a resist line width of approximately 40 μm and a resist line interval of approximately 20 μm.
　こうして得られた銅からなる導体パターンを有するＩＴＯ膜を、以下のように調製した本発明のエッチング液と、比較用エッチング液に浸漬した。 The ITO film having the conductor pattern made of copper thus obtained was immersed in the etching solution of the present invention prepared as follows and a comparative etching solution.
　別途、厚み０．２５ｍｍのＰＥＴ基板上に、スパッタリングによって厚みが１５００ÅのＩＴＯ膜を設け、この膜を、浸漬時間を決定するための標準膜とした。予め、標準膜を表１に示すそれぞれのエッチング液に浸漬し、浸漬開始からＩＴＯ皮膜の溶解が完了した時点までの時間を標準時間（Ｔ）とした。なおＩＴＯ皮膜の溶解完了は、テスターで測定した標準皮膜の表面抵抗値が無限大を示すことで確認した。Ｔが小さいほど、それぞれのエッチング液のエッチング速度が大きいことを示す。 Separately, an ITO film having a thickness of 1500 mm was provided on a PET substrate having a thickness of 0.25 mm by sputtering, and this film was used as a standard film for determining the immersion time. The standard film was previously immersed in each etching solution shown in Table 1, and the time from the start of immersion until the dissolution of the ITO film was completed was defined as the standard time (T). The completion of dissolution of the ITO film was confirmed by the fact that the surface resistance value of the standard film measured with a tester showed infinite. It shows that the etching rate of each etching liquid is so large that T is small.
　表１に示すエッチング液のそれぞれに、銅からなる導体パターンを有するＩＴＯ膜を、Ｔ×１．５に相当する時間をかけて浸漬した。浸漬時に、それぞれのエッチング液の温度を３０℃に維持した。 An ITO film having a conductor pattern made of copper was immersed in each of the etching solutions shown in Table 1 over a time corresponding to T × 1.5. During immersion, the temperature of each etching solution was maintained at 30 ° C.
　このように十分な時間をかけてエッチングを行った。浸漬終了後、銅からなる導体パターンを有するＩＴＯ膜を洗浄、乾燥した。こうして本発明のエッチング液及び比較用エッチング液を用いたエッチング方法を用いて、ＩＴＯ電極パターンが形成された。 Etching was performed in such a sufficient time. After the immersion, the ITO film having a conductor pattern made of copper was washed and dried. Thus, an ITO electrode pattern was formed using an etching method using the etching solution of the present invention and the comparative etching solution.
　（評価）
　実施例１～６、比較例１のエッチング液を用いたエッチング（工程４）を経て、工程３で形成したレジストパターンの形状がＩＴＯ電極パターンとしてどの程度再現されているかを検証した。 (Evaluation)
After the etching using the etching solutions of Examples 1 to 6 and Comparative Example 1 (Step 4), it was verified to what extent the shape of the resist pattern formed in Step 3 was reproduced as an ITO electrode pattern.
　図１は、工程４におけるエッチング直前の、銅からなる導体パターンを表面に有するＩＴＯ膜を模式的に示す。 FIG. 1 schematically shows an ITO film having a conductor pattern made of copper on the surface immediately before etching in step 4.
　エッチング直前のレジスト線間隔（Ｓ１）を異なる４点で測定し、４つの値（Ｓ１１，Ｓ１２，Ｓ１３，Ｓ１４）の平均値（Ｓ１ａｖ）を求めた。 The resist line spacing (S1) immediately before etching was measured at four different points, and the average value (S1av) of the four values (S11, S12, S13, S14) was obtained.
　エッチング直前のレジスト線幅（Ｌ１）を異なる４点で測定し、４つの値（Ｌ１１，Ｌ１２，Ｌ１３，Ｌ１４）の平均値（Ｌ１ａｖ）を求めた。 The resist line width (L1) immediately before etching was measured at four different points, and an average value (L1av) of four values (L11, L12, L13, L14) was obtained.
　図２は、本発明のエッチング液（実施例１～６）を用いて形成された、銅からなる導体パターンを表面に有するＩＴＯ電極パターンを、模式的に表す。図３は、比較用のエッチング液（比較例１）を用いて形成された、銅からなる導体パターンを表面に有するＩＴＯパターンを、模式的に表す。 FIG. 2 schematically shows an ITO electrode pattern having a conductor pattern made of copper on the surface, formed using the etching solution of the present invention (Examples 1 to 6). FIG. 3 schematically shows an ITO pattern having a conductive pattern made of copper on the surface, formed using a comparative etching solution (Comparative Example 1).
　Ｓ１を測定した４点において、エッチング後のＩＴＯパターン線幅（Ｓ２）を測定し、４つの値（Ｓ２１、Ｓ２２、Ｓ２３、Ｓ２４）の平均値（Ｓ２ａｖ）を求めた。 At the four points where S1 was measured, the ITO pattern line width after etching (S2) was measured, and the average value (S2av) of the four values (S21, S22, S23, S24) was determined.
　Ｌ１を測定した４点において、エッチング後のＩＴＯパターン線幅（Ｌ２）を測定し、４つの値（Ｌ２１、Ｌ２２、Ｌ２３、Ｌ２４）の平均値（Ｌ２ａｖ）を求めた。 At the four points where L1 was measured, the ITO pattern line width (L2) after etching was measured, and the average value (L2av) of the four values (L21, L22, L23, L24) was determined.
　実施例１～６、比較例１のエッチング液を用いたエッチングにおける、レジスト線間隔とＩＴＯ電極パターン線間隔の隔たり（ΔＳ）を、式：ΔＳ＝Ｓ１ａｖ－Ｓ２ａｖ　で求めた。実施例１、２、３、４、比較例１に対応するΔＳの値を表１に示す。ΔＳの絶対値が小さいほど、ＩＴＯ膜上の銅導体パターンの腐食が抑えられたことによりＩＴＯ電極パターン線間隔にレジストパターン線間隔がより忠実に再現されていることを意味する。 In the etching using the etching solutions of Examples 1 to 6 and Comparative Example 1, the distance (ΔS) between the resist line interval and the ITO electrode pattern line interval was determined by the formula: ΔS = S1av−S2av. Table 1 shows values of ΔS corresponding to Examples 1, 2, 3, 4, and Comparative Example 1. A smaller ΔS absolute value means that the resist pattern line spacing is more faithfully reproduced in the ITO electrode pattern line spacing because corrosion of the copper conductor pattern on the ITO film is suppressed.
　実施例１～６、比較例１のエッチング液を用いたエッチングにおける、レジスト線幅とＩＴＯ電極パターン線幅の隔たり（ΔＬ）を、式：ΔＬ＝Ｌ１ａｖ－Ｌ２ａｖ　で求めた。実施例１、２、３、４、比較例１に対応するΔＬの値を表１に示す。ΔＬの絶対値が小さいほど、ＩＴＯ膜上の銅導体パターンの腐食が抑えられたことによりＩＴＯ電極パターン線幅にレジストパターン線幅がより忠実に再現されていることを意味する。 The distance (ΔL) between the resist line width and the ITO electrode pattern line width in etching using the etching solutions of Examples 1 to 6 and Comparative Example 1 was determined by the formula: ΔL = L1av−L2av. Table 1 shows values of ΔL corresponding to Examples 1, 2, 3, 4 and Comparative Example 1. It means that the smaller the absolute value of ΔL, the more faithfully the resist pattern line width is reproduced in the ITO electrode pattern line width by suppressing the corrosion of the copper conductor pattern on the ITO film.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示されるように、（ｃ）銅溶解抑制剤を配合した本発明のエッチング液によりＩＴＯ膜が選択的にエッチングされるから、レジストパターンが精度よくＩＴＯ電極パターンに再現される。本発明のエッチング液のこのような選択的エッチング効果は、エッチング液調から少なくとも５時間経過まで、安定している。しかも、本発明のエッチングを用いたエッチングでは、（ｃ）銅溶解抑制剤を用いない比較例１の場合に比べて、エッチング速度は減少しない。 As shown in Table 1, since the ITO film is selectively etched by the etching solution of the present invention containing (c) a copper dissolution inhibitor, the resist pattern is accurately reproduced as an ITO electrode pattern. Such a selective etching effect of the etching solution of the present invention is stable until at least 5 hours have passed since the etching solution was prepared. Moreover, in the etching using the etching of the present invention, the etching rate does not decrease compared to the case of Comparative Example 1 in which (c) the copper dissolution inhibitor is not used.
　［実施例７、実施例８、比較例２］
　表１に示す条件でエッチング液を製造した。実施例８、実施例９では、（ｃ）塩酸ヒドロキシアンモニウムの２０重量％水溶液の添加から２４時間経過後、エッチングした。比較例２では、調製後２４時間経過した母液をエッチングに用いた。 [Example 7, Example 8, Comparative Example 2]
An etching solution was manufactured under the conditions shown in Table 1. In Examples 8 and 9, etching was performed 24 hours after the addition of 20% by weight aqueous solution of (c) hydroxyammonium hydrochloride. In Comparative Example 2, the mother liquor 24 hours after preparation was used for etching.
　実施例８、比較例２のエッチング液を用いて実施例１と同じ条件でエッチングし、評価した。実施例９のエッチング液を用いたエッチングでは、エッチング液の接触方法を浸漬からスプレー法に変え、その他の条件は実施例１と同じで、ＩＴＯ膜をエッチングし、評価した。結果を表２に示す。 Etching was performed under the same conditions as in Example 1 using the etching solutions of Example 8 and Comparative Example 2, and evaluated. In etching using the etching solution of Example 9, the contact method of the etching solution was changed from immersion to spraying, and other conditions were the same as in Example 1, and the ITO film was etched and evaluated. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２に示されるように、本発明のエッチング液の選択的エッチング効果は、エッチング液調製から２４時間を経ても、あるいは、エッチング液とＩＴＯ膜との接触方法が変わっても、維持される。 As shown in Table 2, the selective etching effect of the etching solution of the present invention is maintained even after 24 hours from the preparation of the etching solution or even when the contact method between the etching solution and the ITO film is changed.
　［実施例９］
　実施例９は、エッチング液に（ｃ）塩酸ヒドロキシアンモニウムの２０重量％水溶液を分割添加した例である。実施例９では、表１に示す母液１Ｌに対して２ｍｌの（ｃ）塩酸ヒドロキシアンモニウムの２０重量％水溶液を添加してから２４時間後に、再度先と同量の（ｃ）塩酸ヒドロキシアンモニウムの２０重量％水溶液を添加した。最初の（ｃ）塩酸ヒドロキシアンモニウムの添加から７２時間経過した時点のエッチング液を用いて、実施例１と同じ条件でＩＴＯ膜をエッチングし、評価した。結果を表３に示す。 [Example 9]
Example 9 is an example in which (c) a 20% by weight aqueous solution of hydroxyammonium hydrochloride was added in portions to the etching solution. In Example 9, 2 ml of (c) 20% by weight aqueous solution of hydroxyammonium hydrochloride was added to 1 L of the mother liquor shown in Table 1, and 24 hours later, the same amount of (c) A weight percent aqueous solution was added. The ITO film was etched and evaluated under the same conditions as in Example 1 using the etchant at the time when 72 hours had passed since the first addition of (c) hydroxyammonium hydrochloride. The results are shown in Table 3.
　［実施例１０］
　実施例１０も、エッチング液に（ｃ）塩酸ヒドロキシアンモニウムの２０重量％水溶液を分割添加した例である。実施例１０では、表１に示す母液１Ｌに対して２ｍｌの（ｃ）塩酸ヒドロキシアンモニウムの２０重量％水溶液を添加してから２４時間後、４８時間後に、再度それぞれ先と同量の（ｃ）塩酸ヒドロキシアンモニウムの２０重量％水溶液を添加した。最初の（ｃ）塩酸ヒドロキシアンモニウムの添加から７２時間経過した時点のエッチング液を用いて、実施例１と同じ条件でＩＴＯ膜をエッチングし、評価した。結果を表３に示す。 [Example 10]
Example 10 is also an example in which (c) a 20% by weight aqueous solution of hydroxyammonium hydrochloride was dividedly added to the etching solution. In Example 10, 2 ml of (c) 20% by weight aqueous solution of hydroxyammonium hydrochloride was added to 1 L of the mother liquor shown in Table 1, 24 hours and 48 hours later, again with the same amount of (c) as above. A 20 wt% aqueous solution of hydroxyammonium hydrochloride was added. The ITO film was etched and evaluated under the same conditions as in Example 1 using the etchant at the time when 72 hours had passed since the first addition of (c) hydroxyammonium hydrochloride. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３に示されるように、本発明のエッチング液に（ｃ）銅溶解抑制剤を分割して添加することによって、ＩＴＯ膜に対する選択的エッチング効果の経時劣化を抑制することができる。 As shown in Table 3, deterioration of the selective etching effect with respect to the ITO film over time can be suppressed by adding (c) a copper dissolution inhibitor separately to the etching solution of the present invention.
　［実施例１１、１２］
　実施例１１、１２は（ｅ）酸化剤を添加しなかった例である。表４に示す母液１Ｌに対して（ｃ）塩酸ヒドロキシアンモニウムの２０重量％水溶液２ｍｌを添加して本発明のエッチング液を製造し、実施例１と同じ条件でＩＴＯ膜をエッチングし、評価した。結果を表４に示す。 [Examples 11 and 12]
Examples 11 and 12 are examples in which (e) the oxidizing agent was not added. The etching solution of the present invention was prepared by adding 2 ml of (c) 20% by weight aqueous solution of hydroxyammonium hydrochloride to 1 L of the mother liquor shown in Table 4, and the ITO film was etched and evaluated under the same conditions as in Example 1. The results are shown in Table 4.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表４に示されるように、本発明のエッチング液では、（ｅ）酸化剤を含まない場合でも、（ａ）ハロゲン化水素、（ｂ）ハロゲン化金属、（ｃ）銅溶解抑制剤、（ｄ）希釈剤の配合により高いエッチング速度とＩＴＯに対する選択性を発揮する。 As shown in Table 4, in the etching solution of the present invention, even when (e) an oxidant is not included, (a) hydrogen halide, (b) metal halide, (c) copper dissolution inhibitor, (d ) High etching rate and selectivity for ITO are achieved by blending diluent.
　本発明のエッチング液は、エッチング速度とＩＴＯ膜に対する選択性を兼ね備え、しかも経時劣化の少ない点で、画期的である。このような本発明のエッチング液を用いることにより、銅配線を有する透明電極パターンを効率よく高精度で作成することができる。本発明はより薄型で高精細画像表示が求められる液晶ディスプレイやタッチパネルの製造に貢献することができる。 The etching solution of the present invention is epoch-making in that it has both an etching rate and selectivity for an ITO film and has little deterioration with time. By using such an etching solution of the present invention, a transparent electrode pattern having a copper wiring can be efficiently produced with high accuracy. The present invention can contribute to the manufacture of liquid crystal displays and touch panels that are thinner and require high-definition image display.
１　基板
２　ＩＴＯ膜
３　銅からなる導体パターン
４　レジストパターン
５　ＩＴＯ電極パターン 1 Substrate 2 ITO film 3 Copper conductive pattern 4 Resist pattern 5 ITO electrode pattern

Claims (3)

  1. （ａ）ハロゲン化水素、（ｂ）ハロゲン化金属、（ｃ）銅溶解抑制剤、（ｄ）希釈剤を含み、任意に（ｅ）酸化剤を含んでもよく、
    上記（ａ）ハロゲン化水素は、塩化水素、臭化水素、ヨウ化水素から選ばれる１以上からなり、
    上記（ｂ）ハロゲン化金属は、元素周期表の第１、２、１３族元素のハロゲン化物から選ばれる１以上からなり、
    上記（ｃ）銅溶解抑制剤は、ヒドロキシルアミンとその塩から選ばれる１以上からなり、
    上記（ｄ）希釈剤は、水及び／又は有機溶媒からなり、任意にリン酸類を含んでもよく、
    上記（ｅ）酸化剤は、アルカリ金属及び／又はアルカリ土類金属の塩素酸塩、硝酸塩あるいは亜硝酸塩、過塩素酸、硝酸、過酸化水素、有機過酸化物から選ばれる１以上からなる、
    銅を主成分とする導体パターンを表面に有する透明導電膜のエッチングに用いる、
    エッチング液。     (A) a hydrogen halide, (b) a metal halide, (c) a copper dissolution inhibitor, (d) a diluent, optionally (e) an oxidant,
    The (a) hydrogen halide comprises at least one selected from hydrogen chloride, hydrogen bromide, and hydrogen iodide,
    The metal halide (b) is composed of one or more selected from halides of Group 1, 2, and 13 elements of the periodic table,
    The (c) copper dissolution inhibitor comprises one or more selected from hydroxylamine and a salt thereof,
    The (d) diluent is composed of water and / or an organic solvent, and may optionally contain phosphoric acids,
    The (e) oxidizing agent comprises one or more selected from alkali metal and / or alkaline earth metal chlorates, nitrates or nitrites, perchloric acid, nitric acid, hydrogen peroxide, organic peroxides,
    Used for etching a transparent conductive film having a conductor pattern mainly composed of copper on the surface,
    Etching solution.
  2. 銅を主成分とする導体パターンを表面に有する透明導電膜を、（ａ）ハロゲン化水素、（ｂ）ハロゲン化金属、（ｃ）銅溶解抑制剤、（ｄ）希釈剤を含み、任意に（ｅ）酸化剤を含んでよいエッチング液に接触させる工程を含む、銅を主成分とする導体パターンを表面に有する透明導電膜のエッチング方法であって、
    上記（ａ）ハロゲン化水素は、塩化水素、臭化水素、ヨウ化水素から選ばれる１以上からなり、
    上記（ｂ）ハロゲン化金属は、元素周期表の第１、２、１３族元素のハロゲン化物から選ばれる１以上からなり、
    上記（ｃ）銅溶解抑制剤は、ヒドロキシルアミンとその塩から選ばれる１以上からなり、
    上記（ｄ）希釈剤は、水及び／又は有機溶媒からなり、任意にリン酸類を含んでもよく、
    上記（ｅ）酸化剤は、アルカリ金属及び／又はアルカリ土類金属の塩素酸塩、硝酸塩あるいは亜硝酸塩、過塩素酸、硝酸、過酸化水素、有機過酸化物から選ばれる１以上からなる、
    銅を主成分とする導体パターンを表面に有する透明導電膜のエッチング方法。     A transparent conductive film having a conductor pattern mainly composed of copper on its surface, containing (a) hydrogen halide, (b) metal halide, (c) copper dissolution inhibitor, (d) diluent, and optionally ( e) A method for etching a transparent conductive film having a conductive pattern mainly composed of copper on the surface, the method comprising a step of contacting an etchant that may contain an oxidizing agent,
    The (a) hydrogen halide comprises at least one selected from hydrogen chloride, hydrogen bromide, and hydrogen iodide,
    The metal halide (b) is composed of one or more selected from halides of Group 1, 2, and 13 elements of the periodic table,
    The (c) copper dissolution inhibitor comprises one or more selected from hydroxylamine and a salt thereof,
    The (d) diluent is composed of water and / or an organic solvent, and may optionally contain phosphoric acids,
    The (e) oxidizing agent comprises one or more selected from alkali metal and / or alkaline earth metal chlorates, nitrates or nitrites, perchloric acid, nitric acid, hydrogen peroxide, organic peroxides,
    A method for etching a transparent conductive film having a conductor pattern mainly composed of copper on a surface thereof.
  3. 以下の工程１～４；
    （工程１）基板上に透明導電膜を形成する工程、
    （工程２）上記透明導電膜上に銅を主成分とする導体膜を形成する工程、
    （工程３）上記銅を主成分とする導体膜をエッチングし、透明導電膜上に銅を主成分とする導体パターンを形成する工程、
    （工程４）工程３で得られた銅を主成分とする導体パターンを表面に有する透明導電膜を、（ａ）ハロゲン化水素、（ｂ）ハロゲン化金属、（ｃ）銅溶解抑制剤、（ｄ）希釈剤を含み、任意に（ｅ）酸化剤を含んでよいエッチング液に接触させて、透明導電膜をエッチングし、透明電極パターンを形成する工程、
    を有する、銅を主成分とする導体パターンを表面に有する透明電極パターンの形成方法であって、
    上記工程４において、
    上記（ａ）ハロゲン化水素は、塩化水素、臭化水素、ヨウ化水素から選ばれる１以上からなり、
    上記（ｂ）ハロゲン化金属は、元素周期表の第１、２、１３族元素のハロゲン化物から選ばれる１以上からなり、
    上記（ｃ）銅溶解抑制剤は、ヒドロキシルアミンとその塩から選ばれる１以上からなり、
    上記（ｄ）希釈剤は、水及び／又は有機溶媒からなり、任意にリン酸類を含んでもよく、
    上記（ｅ）酸化剤は、アルカリ金属及び／又はアルカリ土類金属の塩素酸塩、硝酸塩あるいは亜硝酸塩、過塩素酸、硝酸、過酸化水素、有機過酸化物から選ばれる１以上からなる、
    銅を主成分とする導体パターンを表面に有する透明電極パターンの形成方法。     The following steps 1 to 4;
    (Step 1) A step of forming a transparent conductive film on the substrate,
    (Step 2) A step of forming a conductor film containing copper as a main component on the transparent conductive film,
    (Step 3) A step of etching the conductor film containing copper as a main component to form a conductor pattern containing copper as a main component on the transparent conductive film,
    (Step 4) A transparent conductive film having a conductor pattern mainly composed of copper obtained in Step 3 on its surface is obtained by (a) hydrogen halide, (b) metal halide, (c) copper dissolution inhibitor, ( d) a step of forming a transparent electrode pattern by etching a transparent conductive film by contacting with an etchant containing a diluent and optionally (e) an oxidizing agent;
    A method for forming a transparent electrode pattern having a copper-based conductor pattern on the surface,
    In step 4 above,
    The (a) hydrogen halide comprises at least one selected from hydrogen chloride, hydrogen bromide, and hydrogen iodide,
    The metal halide (b) is composed of one or more selected from halides of Group 1, 2, and 13 elements of the periodic table,
    The (c) copper dissolution inhibitor comprises one or more selected from hydroxylamine and a salt thereof,
    The (d) diluent is composed of water and / or an organic solvent, and may optionally contain phosphoric acids,
    The (e) oxidizing agent comprises one or more selected from alkali metal and / or alkaline earth metal chlorates, nitrates or nitrites, perchloric acid, nitric acid, hydrogen peroxide, organic peroxides,
    A method for forming a transparent electrode pattern having a conductor pattern mainly composed of copper on the surface.
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