WO2015146250A1 - Procédé de formation de câblage et solution de gravure - Google Patents

Procédé de formation de câblage et solution de gravure Download PDF

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Publication number
WO2015146250A1
WO2015146250A1 PCT/JP2015/051531 JP2015051531W WO2015146250A1 WO 2015146250 A1 WO2015146250 A1 WO 2015146250A1 JP 2015051531 W JP2015051531 W JP 2015051531W WO 2015146250 A1 WO2015146250 A1 WO 2015146250A1
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Prior art keywords
copper
etching
etching solution
layer
metal oxide
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PCT/JP2015/051531
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English (en)
Japanese (ja)
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知志 斉藤
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メック株式会社
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Publication of WO2015146250A1 publication Critical patent/WO2015146250A1/fr

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    • 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
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/067—Etchants
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0338—Layered conductor, e.g. layered metal substrate, layered finish layer or layered thin film adhesion layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10007—Types of components
    • H05K2201/10128—Display

Definitions

  • the present invention relates to a wiring formation method and an etching solution used therefor.
  • a touch panel display device or the like used in an electronic device has a display area and a frame area provided around the display area. In the frame area, a plurality of wirings drawn from the display area for connection to a circuit for detecting a touch position are formed.
  • Patent Document 1 As a method of forming the wiring in the frame area, for example, as disclosed in Patent Document 1 below, there is a method of forming a wiring by applying a silver paste on the upper surface of an electrode layer containing a metal oxide.
  • a silver paste on the upper surface of an electrode layer containing a metal oxide.
  • it is required to reduce the resistance value of the wiring material in order to cope with a display device of a terminal that is small and requires high performance such as a smartphone or a tablet terminal. Therefore, it has been studied to use copper, which has a lower resistance than silver paste, as a wiring material.
  • a copper layer having a thickness of about several tens of nm to 1 ⁇ m is formed on an electrode layer containing a metal oxide
  • a method of sequentially patterning the electrode layer has been studied. In this method, first, a copper wiring pattern is formed by etching a copper layer on an electrode layer using an etching solution that dissolves copper, and then an etching solution that dissolves a metal oxide without dissolving copper is used. In this method, the electrode layer (metal oxide layer) exposed between the copper wiring patterns is etched to form a laminated wiring pattern including the patterned electrode layer and the copper wiring pattern.
  • a copper layer is formed on an electrode layer containing a metal oxide, and an etching solution that can etch both copper and metal oxide is used to form a copper wiring pattern and to expose the metal oxide exposed between the copper wiring patterns.
  • a method of etching an object in the same etching tank (hereinafter also referred to as “collective etching”) has been studied.
  • collector etching A method of etching an object in the same etching tank
  • the present invention has been made in view of the above-described problems of the prior art, and provides a wiring forming method capable of suppressing side etching of a copper wiring pattern and an etching solution used for the wiring forming method.
  • the temperature of the etching solution was set near the temperature at which the etching solution began to become cloudy, thereby making the side of the copper wiring pattern The inventors have found that etching can be suppressed and have completed the present invention.
  • an etching solution is brought into contact with a part of the copper layer of the laminated plate in which the copper layer is laminated on the base material, and the copper wiring pattern is formed by etching a part of the copper layer.
  • the copper layer has a thickness of 1.5 ⁇ m or less.
  • the etching solution comprises an acidic aqueous solution containing cupric ions 0.1 to 3% by weight, halide ions 0.1 to 30% by weight, and polyalkylene glycol 0.05 to 20% by weight.
  • T ° C. when the temperature at which the etching solution starts to become turbid
  • the temperature of the etching solution when etching the copper layer is set to (T ⁇ 10) ° C. or higher.
  • the wiring formation method of the present invention can also be applied to the formation of a wiring pattern from a laminate that further includes a metal oxide layer interposed between the base material and the copper layer.
  • the etching solution is brought into contact with a portion of the metal oxide layer where the copper wiring pattern is not laminated. Thereby, since the metal oxide layer of the said part is etched, the laminated wiring pattern containing the patterned metal oxide layer and the said copper wiring pattern can be formed.
  • the metal oxide layer includes one or more metal oxides selected from the group consisting of zinc, tin, aluminum, indium, and gallium.
  • the etching solution of the present invention is an etching solution used in the wiring forming method of the present invention, and contains 0.1 to 3% by weight of cupric ions, 0.1 to 30% by weight of halide ions, An acidic aqueous solution containing 0.05 to 20% by weight of alkylene glycol.
  • the “copper layer” in the present invention may be a layer made only of copper or a layer made of a copper alloy containing copper and other metals.
  • “copper” refers to copper or a copper alloy.
  • (A)-(c) is sectional drawing according to process which shows typically one Embodiment of the wiring formation method of this invention. It is the photograph which looked at the colorimetric tube containing the etching solution which can be used for the wiring formation method of the present invention from the upper part, and the colorimetric tube (A) on the left side shows the state before the etching solution starts to become cloudy, and the colorimetric tube on the right side. The color tube (B) shows a state in which the etching solution starts to become cloudy.
  • FIGS. 1 (a) to 1 (c) are cross-sectional views by process schematically showing an embodiment of a wiring forming method of the present invention.
  • a laminate 100 including a base material 1, a metal oxide layer 2, a copper layer 3 and a cap metal layer 4 sequentially formed on the base material 1 is prepared.
  • a resist pattern 5 is formed on the cap metal layer 4 of the laminated plate 100.
  • the laminated plate may not have a cap metal layer on the copper layer. When the cap metal layer is not formed on the copper layer, a resist pattern is formed on the copper layer.
  • the substrate 1 a resin substrate such as a polyethylene terephthalate film (PET film), a glass substrate, or the like can be used.
  • the metal oxide layer 2 is a layer containing an oxide of one or more metals selected from the group consisting of zinc, tin, aluminum, indium and gallium, and is an undercoat made of SiO 2 or the like directly on the substrate 1. It is provided via a layer or the like.
  • a method of providing the metal oxide layer 2 on the substrate for example, a known method such as vacuum deposition or sputtering can be employed.
  • a preferable thickness of the metal oxide layer 2 is about 5 to 200 nm.
  • the metal oxide constituting the metal oxide layer 2 may be a single metal oxide or a complex metal oxide.
  • ZnO, SnO 2 , Al 2 O 3 , indium tin oxide (ITO), indium zinc oxide (IZO), or a composite metal oxide in which a different metal is doped into ZnO can be used.
  • the composite metal oxide in which a different metal is doped in ZnO include AZO doped with aluminum and GZO doped with gallium.
  • one or more metal oxides selected from the group consisting of zinc, tin, and aluminum are preferable from the viewpoint of pattern formation, and one or more metal oxides selected from ITO, IZO, AZO, and GZO are more preferable.
  • the metal oxide may be either an amorphous or crystalline metal oxide.
  • the crystalline metal oxide is preferable because conductivity and durability are improved.
  • copper is more easily etched than the metal oxide in the conventional etching solution. Therefore, when the metal oxide is etched, the copper wiring pattern 7 (see FIG. 1B). ) Side etching was difficult to suppress. According to the wiring forming method of the present embodiment, side etching of the copper wiring pattern 7 can be suppressed even if the metal oxide is crystalline.
  • the metal oxide is crystalline can be determined by, for example, observing the surface of the metal oxide with a field emission transmission electron microscope (FE-TEM).
  • FE-TEM field emission transmission electron microscope
  • the metal oxide is crystalline, it can be observed as, for example, polygonal or oval crystal grains.
  • the crystalline metal oxide means that the proportion of the area occupied by the crystal grains exceeds 50% when the surface of the metal oxide is observed with the field emission transmission electron microscope (FE-TEM).
  • FE-TEM field emission transmission electron microscope
  • a metal oxide in which the area ratio occupied by the crystal grains is 70% to 100% is preferable.
  • the copper layer 3 can be formed on the metal oxide layer 2 by a known method such as vacuum deposition or sputtering. From the viewpoint of suppressing side etching of the copper wiring pattern 7, the thickness of the copper layer 3 is 1.5 ⁇ m or less, preferably 1.0 ⁇ m or less, more preferably 0.8 ⁇ m or less, and 0.5 ⁇ m. More preferably, it is as follows. Moreover, it is preferable that the thickness of the copper layer 3 is 0.01 micrometer or more from a viewpoint of suppressing high resistance of copper wiring.
  • the wiring in the frame area of the touch panel display device can function sufficiently even when the thickness of the copper layer 3 is small as described above because the current flowing through the circuit is smaller than the wiring of a printed wiring board or the like.
  • a cap metal layer 4 is provided on the copper layer 3 as necessary for rust prevention of the copper layer 3 or the like.
  • the material of the cap metal layer 4 include aluminum, titanium, chromium, cobalt, nickel, zinc, molybdenum, silver, and alloys of these metals and copper.
  • the cap metal layer 4 is preferably made of a copper alloy different from the material of the copper layer 3 or a metal other than copper.
  • nickel, molybdenum, and alloys of these metals and copper are preferable.
  • a nickel-copper alloy having a nickel / copper weight ratio of 30/70 to 70/30 is preferable.
  • the cap metal layer 4 may be composed of a single layer or a plurality of layers.
  • the thickness of the cap metal layer 4 is preferably about 5 to 200 nm.
  • Examples of the method for forming the cap metal layer 4 include known methods such as vacuum deposition and sputtering.
  • a copper wiring pattern 7 shown in FIG. 1B is formed by contacting the copper layer 3 with a later-described etching solution (hereinafter simply referred to as “this etching solution”) under conditions described later. Further, the metal shown in FIG. 1C is obtained by bringing the etching solution into contact with a portion of the metal oxide layer 2 where the copper wiring pattern 7 is not laminated (exposed portion 8 in FIG. 1B) under the conditions described later. By forming the oxide wiring pattern 9, a laminated wiring pattern 10 including the metal oxide wiring pattern 9 and the copper wiring pattern 7 is obtained.
  • the etching solution is brought into contact with the cap metal layer 4 before bringing the etching solution into contact with the copper layer 3, as shown in FIG.
  • a cap metal wiring pattern 6 is formed.
  • the multilayer wiring pattern 10 has a cap metal wiring pattern 6 on the copper wiring pattern 7 as shown in FIG.
  • a laminated wiring pattern 10 having a predetermined shape is obtained by bringing the etching solution into contact with a region where the resist pattern 5 on the surface of the laminated plate 100 is not laminated.
  • side etching of the copper wiring pattern 7 can be suppressed, and side etching of the cap metal wiring pattern 6 when forming the copper wiring pattern 7 can also be suppressed. Further, side etching of the cap metal wiring pattern 6 and the copper wiring pattern 7 when forming the metal oxide wiring pattern 9 can also be suppressed. Thereby, thinning of the line width W1 of the cap metal wiring pattern 6 and the line width W2 of the copper wiring pattern 7 can be suppressed.
  • the copper wiring pattern 7 is formed by galvanic corrosion. There was a risk of side etching progressing. However, according to the wiring forming method of the present embodiment, side etching of the copper wiring pattern 7 can be suppressed even when the cap metal layer 4, which is a dissimilar metal, is formed on the copper layer 3.
  • the cap metal layer 4 is etched to form a cap metal wiring pattern 6 by bringing the etching solution into contact with a region where the resist pattern 5 on the surface of the laminated plate 100 is not laminated.
  • This etching solution comes into contact with the exposed portion of the copper layer 3 formed by etching 4 to etch the copper layer 3, thereby forming a copper wiring pattern 7.
  • the etching solution comes into contact with the exposed portion 8 of the metal oxide layer 2 formed by etching the copper layer 3 to etch the metal oxide layer 2, thereby forming a metal oxide wiring pattern 9.
  • This etchant has etchability for both copper and metal oxides. Therefore, after the copper layer 3 is etched and the copper wiring pattern 7 is formed, the metal oxide layer 2 may be subsequently etched. That is, in this embodiment, the contact of the main etching solution with the copper layer 3 and the contact of the main etching solution with the metal oxide layer 2 can be performed as a series of steps.
  • the cap metal layer 4 etching process, the copper layer 3 etching process, and the metal oxide layer 2 etching process may be performed in the same etching tank or in different etching tanks. Also good. It is preferable to treat the cap metal layer 4, the copper layer 3, and the metal oxide layer 2 in the same etching tank because the number of etching steps can be reduced and the management of the etching solution is simplified.
  • the composition of the etching solution used in each of the etching tanks is the same composition. Alternatively, different compositions may be used. Further, each of the plurality of etching tanks need not correspond to the etching process of the cap metal layer 4, the copper layer 3, and the metal oxide layer 2. For example, in the first etching tank, in addition to the cap metal layer 4 and the copper layer 3, a part of the metal oxide layer 2 in the depth direction is etched, and then the metal oxide in the second etching tank. The layer 2 may be further etched to form the metal oxide wiring pattern 9.
  • This etching solution is an etching solution comprising an acidic aqueous solution containing 0.1 to 3% by weight of cupric ions, 0.1 to 30% by weight of halide ions, and 0.05 to 20% by weight of polyalkylene glycol. is there.
  • this etching liquid can etch not only copper but the cap metal used for copper rust prevention, a metal oxide, etc.
  • cupric ion contained in this etching liquid is mix
  • the cupric ion can be contained in the etching solution by blending a cupric ion source.
  • the cupric ion source include one or more selected from cupric chloride, cupric sulfate, cupric bromide, cupric salts of organic acids, and cupric hydroxide.
  • the concentration of the cupric ion is 0.1 to 3% by weight, preferably 0.2 to 2% by weight, and more preferably 0.2 to 1% by weight. If the concentration is 0.1% by weight or more, the etching rate is increased, so that copper can be etched quickly. Moreover, when the said density
  • Halide ion (Halide ion) Halide ions contained in this etching solution are blended as a component that promotes copper etching.
  • the halide ions also function as a component for removing the metal oxide when etching an etching object in which copper and the metal oxide coexist.
  • Examples of the halide ion include one or more selected from fluoride ion, chloride ion, bromide ion, and iodide ion, and chloride ion and bromide ion are preferred from the viewpoint of copper etching property and handleability. Chloride ions are more preferred.
  • Halide ions include, for example, acids such as hydrochloric acid and hydrobromic acid, sodium chloride, ammonium chloride, calcium chloride, potassium chloride, potassium bromide, sodium fluoride, potassium iodide, cupric chloride, and bromide.
  • acids such as hydrochloric acid and hydrobromic acid
  • sodium chloride ammonium chloride
  • calcium chloride potassium chloride, potassium bromide, sodium fluoride, potassium iodide
  • cupric chloride and cupric bromide can be used as those having the functions of both a halide ion source and a cupric ion source.
  • the concentration of halide ions in this etching solution is 0.1 to 30% by weight, preferably 1 to 25% by weight, and more preferably 2 to 20% by weight. If the said density
  • the polyalkylene glycol contained in the etching solution is blended as a component that suppresses side etching of the copper wiring pattern 7.
  • the etching solution is set to a predetermined temperature range described later and etched, the polyalkylene glycol contained in the etching solution adheres to the side surface of the copper wiring pattern 7, It is presumed that the attached polyalkylene glycol functions as a protective film that suppresses side etching.
  • the etching solution is brought into contact with the exposed portion 8 of the metal oxide layer 2 formed by etching the copper layer 3 to etch the metal oxide layer 2.
  • polyalkylene glycol examples include one or more selected from polyethylene glycol, polypropylene glycol, polybutylene glycol, and the like. From the viewpoint of suppressing side etching, polypropylene glycol and polybutylene glycol are preferable, and polypropylene glycol is more preferable. Polypropylene glycol is also preferably used from the viewpoint of controlling the turbidity of the etching solution described later to 70 ° C. or lower, keeping the etching temperature low, and suppressing deterioration of the working environment due to odor and the like. The surfactant in which a hydrophobic molecule is bonded to the polyalkylene oxide group is not included in the polyalkylene glycol.
  • the weight average molecular weight of the polyalkylene glycol is preferably 200 to 5000, more preferably 400 to 4000, from the viewpoint of suppressing side etching. Moreover, if it is the range of this weight average molecular weight, the said protective film can be easily removed by the water washing process etc. in the next process after forming the copper wiring pattern 7.
  • the concentration of polyalkylene glycol in the etching solution is 0.05 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight. If the concentration is 0.05% by weight or more, side etching can be suppressed. Moreover, if the said density
  • This etchant is an acidic aqueous solution.
  • the acid to be blended to make the etching solution acidic is not particularly limited.
  • sulfonic acid compounds such as methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and taurine; hydrochloric acid, odor
  • inorganic acids such as hydrofluoric acid, sulfuric acid, nitric acid, borohydrofluoric acid, and phosphoric acid
  • carboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid.
  • the preferred concentration of the acid is preferably 0.003 to 1.0% by weight as the H + concentration, more preferably 0.03 to 1.0% by weight, still more preferably 0.06 to 1.0% by weight. It is.
  • the concentration is 0.003% by weight or more, the etching rate increases, so that copper can be etched quickly.
  • concentration is 1.0 weight% or less, the melt
  • the acid concentration is preferably within the above range. In particular, in the case of etching an etching object in which copper and a crystalline metal oxide coexist, if the H + concentration is in the range of 0.2 to 1.0% by weight, in addition to the etching property of copper.
  • the etching property of the metal oxide can be improved.
  • an inorganic acid is preferably used as the acid.
  • hydrochloric acid or hydrobromic acid it is preferable because the etching solution is adjusted to be acidic and at the same time the halide ion source is used.
  • This etching solution can be easily prepared by dissolving the above-described components in water.
  • water water from which ionic substances and impurities have been removed is preferable.
  • ion-exchanged water, pure water, ultrapure water, and the like are preferable.
  • additives such as a stabilizer, to this etching liquid as needed.
  • etching solution for example, a method of spraying the etching solution on a region where the resist pattern 5 on the surface of the laminated plate 100 is not laminated, or the laminated plate 100 provided with the resist pattern 5.
  • the method etc. which are immersed in this etching liquid are mentioned.
  • etching by spraying it is preferable to keep the temperature of the etching solution within the range described later and to perform the treatment at a spray pressure of 0.03 to 0.3 MPa.
  • etching is performed by dipping, the etching is performed while keeping the temperature of the etching solution within a range described later.
  • FIG. 2 is a photograph of the colorimetric tube containing the present etching solution at a height of 20 cm from the bottom as seen from above, and the left colorimetric tube (A) shows the state before the present etching solution begins to become cloudy.
  • the right colorimetric tube (B) shows a state in which the etching solution starts to become cloudy by heating.
  • the etching solution starts to become cloudy, and the temperature at which the bottom of the colorimetric tube cannot be visually recognized is defined as the cloudy point.
  • the temperature of the etching solution when etching the copper layer 3 is set to (T ⁇ 10) ° C. or more.
  • T ⁇ 10 ° C. or more the temperature of the etching solution when etching the copper layer 3 is set to (T ⁇ 10) ° C. or more.
  • the temperature of this etching solution when etching the copper layer 3 is preferably (T-7) ° C. or higher, more preferably (T-5) ° C. or higher, from the viewpoint of suppressing side etching.
  • the temperature of the etching solution when etching the copper layer 3 is preferably (T + 10) ° C. or less, more preferably (T + 5) ° C. or less. It is.
  • the metal oxide layer 2 is It is preferable that the temperature of the etching solution at the time of etching is also within the above range. As a result, even when the metal oxide layer 2 is etched, the state in which the polyalkylene glycol contained in the etching solution is adhered to the side surface of the copper wiring pattern 7 is maintained, so that side etching of the copper wiring pattern 7 is suppressed. Is done.
  • the copper layer 3 and the metal oxide layer 2 are processed in the same etching tank, and the contact of the etchant with the copper layer 3 and the contact of the etchant with the metal oxide layer 2 are performed as a series of steps. If implemented, management of the etching temperature (liquid temperature and atmospheric temperature) can be simplified, which is preferable.
  • the turbidity of the etching solution can be controlled by adjusting the weight average molecular weight, acid concentration, etc. of the polyalkylene glycol to be blended. That is, the turbidity point of the present etching solution decreases as the weight average molecular weight of the polyalkylene glycol increases, and increases as the acid concentration (H + concentration) increases. Moreover, a turbidity point can also be lowered
  • the etching solution when used continuously or repeatedly, it is preferable to perform etching while adding a replenishing solution made of an acidic aqueous solution containing halide ions and polyalkylene glycol.
  • a replenishing solution made of an acidic aqueous solution containing halide ions and polyalkylene glycol.
  • the halide ions, polyalkylene glycol, and acid added to make the replenisher acidic in the replenisher are the same as those contained in the etching solution described above.
  • the replenishing solution may further contain a cupric ion source such as cupric chloride in a range not exceeding 0.7% by weight in terms of cupric ion concentration.
  • the replenishing solution may contain a component added to the etching solution.
  • the concentration of each component in the replenisher is appropriately set according to the concentration of each component in the etching solution.
  • the concentration of halide ions is It is preferable that the concentration is 0.1 to 30% by weight, the polyalkylene glycol concentration is 0.05 to 20% by weight, and the acid concentration is 0.03 to 1.0% by weight as the H + concentration.
  • the cap metal layer is etched with the above-described etchant, but may be etched with an etchant different from the present etchant.
  • the description has been made mainly on the example in which the cap metal layer is provided.
  • the wiring forming method of the present invention the laminate plate without the cap metal layer, the cap metal layer, and the metal oxide layer are provided. A laminated board that is not provided may be used.
  • the wiring forming method of the present invention can be applied to various wiring forming methods including a step of etching a copper layer having a thickness of 1.5 ⁇ m or less.
  • the laminate is immersed in a 10% by weight sulfuric acid aqueous solution (temperature: 25 ° C.) for 1 minute to remove the oxide on the surface of the nickel-copper alloy layer, and then a dry film resist (product number ATP-) is formed on the surface of the nickel-copper alloy layer.
  • a resist pattern of line / space 30 ⁇ m / 30 ⁇ m was formed.
  • the temperature of each etching solution is set to the processing temperature described in Tables 1-1 and 1-2, and the laminate is sprayed. , Washed with water and dried.
  • the spray pressure was set to 0.08 MPa, and a spray nozzle (product number 040) manufactured by Ikeuchi Co., Ltd. was used.
  • the spray processing time was 120 seconds and 360 seconds.
  • the spray treatment time is set to 360 seconds, the presence or absence of the side etching suppression effect becomes clearer.
  • each laminated plate after drying was observed with a scanning electron microscope (model JSM-7000F, manufactured by JEOL Ltd.), and the metal oxidation shown in FIG.
  • the ITO layer between the ITO wiring patterns corresponding to the object wiring pattern 9 has been removed.
  • each of the examples in which an etching solution composed of an acidic aqueous solution containing polyalkylene glycol was used and etching was performed in a specific temperature range had a side etching amount.
  • the overall evaluation was A or B.
  • the amount of side etching was larger than that in the examples, and the overall evaluation was C.
  • Example 13 has a high acid concentration, and although the etching is performed under stronger conditions, the amount of side etching is the same as that of Examples 11 and 12. It can also be seen that there are fewer than those in Examples 11 and 12. Moreover, the same tendency is seen in the comparison between Examples 19 and 20 and Example 21. Thus, even if a high concentration acid is used, side etching of the copper wiring pattern can be suppressed. Therefore, the wiring forming method of the present invention has a high acid concentration (for example, 0.2% by weight or more as H + concentration). In the case of forming a multilayer wiring pattern including a patterned metal oxide layer and a copper wiring pattern by performing etching of a crystalline metal oxide and a copper layer which require a It turns out that it can apply suitably.
  • a high acid concentration for example, 0.2% by weight or more as H + concentration
  • a laminate including a laminated wiring pattern was obtained in the same procedure as described above [Evaluation of laminate comprising PET film / ITO layer / copper layer / nickel-copper alloy layer]. Each of the obtained laminates was observed with a scanning electron microscope (model JSM-7000F, manufactured by JEOL Ltd.), and the metal oxide wiring shown in FIG. The IZO layer between the IZO wiring patterns corresponding to the pattern 9 has been removed.
  • each example had a small amount of side etching and the overall evaluation was A or B, whereas each comparative example had a side etching amount.
  • the amount of etching increased compared to the examples, and the overall evaluation was C. From these results, it can be seen that by using the method of the present invention, the side etching amount of the copper wiring can be reduced regardless of the material of the metal oxide layer or the cap metal layer.

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Abstract

L'objet de la présente invention est de fournir un procédé de formation de câblage qui permet la réduction au minimum du côté gravure d'un motif de câblage de cuivre et une solution de gravure devant être utilisé en son sein. Ce procédé de formation de câblage consiste à mettre en contact une solution de gravure et une partie d'une couche de cuivre (3) d'une plaque en couches (100) obtenue par superposition de la couche de cuivre (3) sur un substrat (1) et former un motif de câblage en cuivre (7) par gravure de l'une partie de la couche de cuivre (3). La couche de cuivre (3) présente une épaisseur inférieure ou égale à 1,5 μm. La solution de gravure est une solution aqueuse acide contenant de 0,1 à 3 % en poids d'un ion cuivrique, de 0,1 à 30 % en poids d'un ion halogénure, et de 0,05 à 20 % en poids de polyalkylène glycol. Ce procédé de formation de câblage consiste à régler la température de la solution de gravure lors de la gravure de la couche de cuivre (3) à une valeur supérieure ou égale à (T-10) °C. T est la température à laquelle la solution d'attaque commence à devenir trouble.
PCT/JP2015/051531 2014-03-28 2015-01-21 Procédé de formation de câblage et solution de gravure WO2015146250A1 (fr)

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