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CN109797396B - Silver film etching liquid composition, etching method using the same and metal pattern forming method - Google Patents

Silver film etching liquid composition, etching method using the same and metal pattern forming method Download PDF

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CN109797396B
CN109797396B CN201811060633.6A CN201811060633A CN109797396B CN 109797396 B CN109797396 B CN 109797396B CN 201811060633 A CN201811060633 A CN 201811060633A CN 109797396 B CN109797396 B CN 109797396B
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silver
etching
indium oxide
etching solution
thin film
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CN109797396A (en
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沈庆辅
金童基
尹暎晋
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Dongwoo Fine Chem Co Ltd
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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
    • C23F1/30—Acidic compositions for etching other metallic material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
    • 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
    • C23F1/02—Local etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • ing And Chemical Polishing (AREA)
  • Weting (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The present invention relates to a silver thin film etchant composition, an etching method using the same, and a metal pattern forming method, the silver thin film etchant composition including an organic acid, an inorganic acid, an etching initiator, and the balance of water, and having an etch stop index of 0.05 to 0.35.

Description

Silver film etching liquid composition, etching method using the same and metal pattern forming method
Technical Field
The present invention relates to a silver thin film etching solution composition, an etching method using the same, and a metal pattern forming method, wherein the silver thin film etching solution composition comprises an organic acid, an inorganic acid, an etching initiator, and water, and has an etch stop index of 0.05 to 0.35.
Background
As the information age is really advanced, the field of displays for processing and displaying a large amount of information is rapidly developed, and accordingly, various flat panel displays have been developed and are receiving attention.
Examples of such flat Panel Display devices include Liquid crystal Display devices (LCD), Plasma Display devices (PDP), Field Emission Display devices (FED), electroluminescent Display devices (ELD), Organic Light Emitting Display devices (OLED), and the like, and such flat Panel Display devices are used for various purposes not only in the fields of televisions, video recorders, and the like, but also in computers such as notebooks, mobile phones, and the like. These flat panel display devices have rapidly replaced the conventional Cathode Ray tubes (NITs) because of their excellent performance such as reduction in thickness, weight, and power consumption.
In particular, since an OLED (organic light emitting diode) element itself emits light and can be driven even at a low voltage, the OLED is rapidly applied to a small display market such as a portable device in recent years. In addition, the OLED is in a state of being commercialized over a small display to realize a large TV.
Further, conductive metals such as Indium Tin Oxide (ITO) and Indium Zinc Oxide (IZO) have relatively excellent transmittance to light and conductivity, and thus are widely used as electrodes of color filters used in flat panel display devices. However, these metals also have high resistance, and are an obstacle to achieving large-scale and high-resolution flat panel display devices by improving response speed.
In the case of the reflecting plate, an aluminum (Al) reflecting plate has been mainly used as a product in the past, but in order to improve brightness and realize low power consumption, a metal changing material having a higher reflectance is searched for. Accordingly, it is desired to realize the large size, high resolution, low power consumption, and the like of a flat panel display device by applying a silver (Ag: specific resistance about 1.59. mu. omega. cm) film, a silver alloy, or a multilayer film comprising the silver alloy having a lower specific resistance and higher luminance than metals applied to the flat panel display device to electrodes of color filters, LCD or OLED wirings, and a reflective plate, and accordingly, development of an etching solution for applying the material is required.
However, silver (Ag) has very poor adhesion (adhesion) to an insulating substrate such as glass or a lower substrate such as a semiconductor substrate made of intrinsic amorphous silicon or doped amorphous silicon, and thus deposition is not easily performed, and floating (lifting) or Peeling (Peeling) of a wiring is easily induced. Further, even in the case where a silver (Ag) conductive layer is deposited on a substrate, in order to perform patterning of the silver conductive layer, an etching solution needs to be used. When a conventional etching solution is used as such an etching solution, the silver (Ag) is excessively etched or unevenly etched, and thus a floating or peeling phenomenon of the wiring occurs, resulting in a poor profile of the side surface of the wiring.
Further, it is difficult to perform a LOW Skew (LOW Skew) realization process for realizing high resolution.
Particularly, silver (Ag) is a metal that is easily reduced, and is etched without generating a residue due to its high etching rate, but in this case, a difference in etching rate between upper and lower portions does not occur due to its high etching rate, it is difficult to form a taper angle (taper angle) after etching, and it is difficult to ensure straightness of each pattern, and there are many limitations in applying silver to a wiring.
When the metal film is vertically raised without a taper angle (taper angle), there is a possibility that a void may be generated between silver (Ag) and an insulating film or a wiring when the insulating film or the subsequent wiring is formed in the subsequent process, and the void may cause a defect such as an electrical short circuit.
Thus, studies for improving etching characteristics are actively conducted, and as a representative example, a silver etchant composition containing nitric acid, phosphoric acid, acetic acid, an auxiliary oxide dissolving agent, a fluorine-containing carbon-based surfactant, and water is proposed in korean patent laid-open No. 10-579421, but the Ag over-etching problem and the re-adsorption problem cannot be completely solved in this technical field. Thus, there has been a demand for development of an etching solution composition capable of improving etching characteristics for silver, and active research has been conducted in response to the demand, but an etching solution composition having significantly improved etching characteristics as compared with the prior art has not been proposed.
Documents of the prior art
Patent document
Patent document 1: korean granted patent No. 10-0579421
Disclosure of Invention
Technical problem
An object of the present invention is to provide a silver thin film etching solution composition for etching a single layer film composed of silver or a silver alloy or a multi-layer film composed of the single layer film and an indium oxide film, which has an appropriate etching rate without problems of occurrence of residues (e.g., silver residues and/or indium oxide film residues) and silver re-adsorption, thereby reducing side etching.
In addition, the invention provides an etching method using the silver thin film etching solution composition.
In addition, the present invention provides a method for forming a metal pattern using the silver thin film etchant composition. Means for solving the problems
In order to achieve the above object, the present invention relates to a silver thin film etching solution composition and an etching method using the same, and more particularly, to a silver thin film etching solution composition comprising 40 to 65 wt% of an organic acid, 5 to 10 wt% of an inorganic acid, 1 to 15 wt% of an etching initiator, and the balance of water to make the total weight of the composition 100 wt%, based on the total weight of the composition.
Further, the present invention provides an etching method comprising the steps of: forming a single-layer film composed of silver or a silver alloy or a multilayer film composed of the single-layer film and an indium oxide film on a substrate; selectively leaving a photoreactive substance on the single layer film composed of silver or a silver alloy or a multilayer film composed of the single layer film and an indium oxide film; and etching the single-layer film composed of silver or a silver alloy or a multi-layer film composed of the single-layer film and an indium oxide film by using the silver thin film etching solution composition.
Further, the present invention provides a method of forming a metal pattern, comprising the steps of: forming a single-layer film composed of silver or a silver alloy or a multilayer film composed of the single-layer film and an indium oxide film; selectively leaving a photoreactive substance on the single layer film composed of silver or a silver alloy or a multilayer film composed of the single layer film and an indium oxide film; and etching the single-layer film composed of silver or a silver alloy or a multi-layer film composed of the single-layer film and an indium oxide film by using the silver thin film etching solution composition.
Effects of the invention
The silver thin film etching solution composition of the present invention has an appropriate etching rate without problems of residue generation (e.g., silver residue and/or indium oxide film residue) and silver re-adsorption, and thus has an effect of reducing side etching, and accordingly has an excellent effect as a silver thin film etching solution composition for etching a single layer film composed of silver or a silver alloy or a multi-layer film composed of the single layer film and an indium oxide film.
Detailed Description
The present invention will be described in more detail below.
The invention relates to a silver thin film etching solution composition, which comprises 40-65 wt% of organic acid, 5-10 wt% of inorganic acid, 1-15 wt% of etching initiator and the balance of water for making the total weight of the composition be 100 wt% relative to the total weight of the composition.
The present invention has been accomplished by the finding that the present invention has an appropriate etching rate without the occurrence of the problem of residue (e.g., silver residue and/or indium oxide film residue) and the problem of silver re-adsorption, and thus has a reduced Side etching (Side Etch) and exhibits an excellent effect as a silver thin film etching solution composition for etching a single layer film composed of silver or a silver alloy or a multilayer film composed of the single layer film and an indium oxide film.
Specifically, the etching liquid composition of the present invention is characterized in that the etch stop index calculated in the following manner is 0.05 to 0.35,
etch stop index ═ inorganic acid + initiator)/(organic acid + water).
The etching stop index is an index of a ratio of contents of an inorganic acid and an initiator for increasing an etching rate (Etch rate) to an organic acid for chelating a metal, and it was experimentally confirmed that when a single layer film composed of silver or a silver alloy or a multilayer film composed of the single layer film and an indium oxide film is etched at an etching stop index of 0.05 to 0.35, there are an appropriate etching rate without causing a problem of residue (for example, silver residue and/or indium oxide film residue) and a problem of silver re-adsorption, and thus there is an effect of reducing side etching.
The silver thin film etching solution composition of the present invention is characterized in that a single layer film composed of silver (Ag) or a silver alloy or a multilayer film composed of the single layer film and an indium oxide film can be etched, and the silver thin film etching solution composition can simultaneously etch the multilayer film.
The silver alloy contains silver as a main component, and may have various forms including an alloy form of other metals such as Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W, and Ti, and a nitride, silicide, carbide, and oxide form of silver, but is not limited thereto.
In addition, the indium oxide is one or more selected from the group consisting of Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), Indium Tin Zinc Oxide (ITZO), and Indium Gallium Zinc Oxide (IGZO).
Further, the multi-layered film may be a multi-layered film formed of an indium oxide film/silver, an indium oxide film/silver alloy, an indium oxide film/silver/indium oxide film, or an indium oxide film/silver alloy/indium oxide film, and in the case of using the silver thin film etching solution composition of the present invention, has an appropriate etching rate without having a residue (e.g., silver residue and indium oxide film residue) generation problem and a silver re-adsorption problem, and thus does not cause side etching, and can be effectively applied to wet etching.
The organic acid contained in the silver thin film etching solution composition of the present invention is a component used as a main oxidant, and performs a role of performing wet etching by oxidizing silver (Ag) and a transparent conductive film in the transparent conductive film/Ag/transparent conductive film.
The organic acid is contained in an amount of 40 to 65 wt%, preferably 43 to 63 wt%, with respect to the total weight of the silver thin film etching solution composition.
When the content of the organic acid is less than 40% by weight based on the total weight of the composition, there is a possibility that problems may occur due to a decrease in the etching rate of silver and the generation of silver residue, and when the content of the organic acid is more than 65% by weight based on the total weight of the composition, there is a possibility that an overetching phenomenon may occur due to an excessively high etching rate of the transparent conductive film and an excessively high etching rate of silver, thereby causing problems in subsequent processes.
The organic acid contained in the silver thin film etching solution of the present invention may be one or more selected from the group consisting of acetic acid, butyric acid, citric acid (citric acid), formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, valeric acid, methanesulfonic acid, benzenesulfonic acid, sulfosuccinic acid, sulfophthalic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, succinic acid, malic acid, tartaric acid, isocitric acid, acrylic acid, iminodiacetic acid, and ethylenediaminetetraacetic acid, and more preferably may contain acetic acid and citric acid.
The inorganic acid contained in the silver thin film etching solution composition of the present invention is a component used as an etching improver, and performs a role of performing wet etching by oxidizing silver (Ag) and a transparent conductive film in the transparent conductive film/Ag/transparent conductive film.
The inorganic acid is contained in an amount of 5 to 10 wt%, preferably 6 to 9 wt%, based on the total weight of the silver thin film etching solution composition.
When the content of the inorganic acid is less than 5 wt% with respect to the total weight of the composition, the etching rate of the silver (Ag) and the transparent conductive film is decreased, thereby deteriorating the etching uniformity within the substrate and generating the stripe, and when the content of the inorganic acid is more than 10 wt% with respect to the total weight of the composition, there is a disadvantage that the etching rate of the upper and lower transparent conductive films and the Ag film is increased to generate the over-etching and the pattern loss phenomenon is generated.
The inorganic acid contained in the silver thin film etching solution of the present invention may be one or more selected from the group consisting of nitric acid, sulfuric acid, and hydrochloric acid.
The etching initiator contained in the silver thin film etching solution composition of the present invention is a component used as an etching rate modifier, and performs an action of accelerating an etching rate with respect to an oxide and Ag metal.
The etching initiator is contained in an amount of 1 to 15 wt%, preferably 3 to 12 wt%, with respect to the total weight of the silver thin film etching solution composition.
If the content of the etching initiator is less than 1 wt% with respect to the total weight of the composition, the etching rate is slow, and if the content of the etching initiator is more than 15 wt% with respect to the total weight of the composition, the etching rate may increase to cause a problem in a subsequent process due to the occurrence of a Tip (Tip) of the upper transparent conductive film.
The etching initiator contained in the silver thin film etching solution of the present invention may be one or more selected from the group consisting of peroxide initiators, alkali metal initiators, and transition metal initiators.
The peroxide initiator may be one or more selected from the group consisting of sodium persulfate, ammonium persulfate, potassium monopersulfate complex salt, and oxalic acid.
The alkali metal initiator may be one or more selected from the group consisting of sodium nitrate, potassium nitrate, calcium nitrate, sodium sulfate, potassium sulfate, calcium sulfate, sodium chloride, calcium chloride and potassium chloride.
The transition metal initiator may be one or more selected from the group consisting of ferrous nitrate, ferric nitrate, ferrous sulfate, and ferric sulfate.
As water contained in the silver thin film etching liquid composition of the present invention, deionized water for semiconductor processes can be used, and preferably, water of 18M Ω/cm or more can be used, and the balance water is contained so that the total weight of the composition becomes 100 wt%.
The silver thin film etchant composition of the present invention can be effectively used as a wet etchant using a single-layer film of a silver/silver alloy or a multi-layer structure using two or more films of the single-layer film and an indium oxide film, etc., which are widely used for forming a TFT array substrate of a display (OLED, LCD, etc.), a TSP (touch screen panel) Trace wiring, and a Flexible (flex) nanowire wiring. In addition, the present invention can be applied to electronic component materials using the metal film material, such as semiconductors, in addition to the above-mentioned displays and TSPs.
Furthermore, the invention relates to an etching method comprising the steps of:
forming a single-layer film composed of silver or a silver alloy or a multilayer film composed of the single-layer film and an indium oxide film on a substrate;
selectively leaving a photoreactive substance on the single layer film composed of silver or a silver alloy or a multilayer film composed of the single layer film and an indium oxide film; and
the single-layer film composed of silver or a silver alloy or a multi-layer film composed of the single-layer film and an indium oxide film is etched using the silver thin film etching liquid composition.
Further, the present invention relates to a method of forming a metal pattern, comprising the steps of:
forming a single-layer film composed of silver or a silver alloy or a multilayer film composed of the single-layer film and an indium oxide film; and
the single-layer film composed of silver or a silver alloy or a multi-layer film composed of the single-layer film and an indium oxide film is etched using the silver thin film etching liquid composition.
The present invention will be described in more detail below with reference to examples. However, the following examples are intended to more specifically illustrate the present invention, and the scope of the present invention is not limited by the following examples. Those skilled in the art can appropriately modify and change the following embodiments within the scope of the present invention.
<Preparation of silver thin film etching solution composition>
Examples 1 to 7 and comparative examples 1 to 3
Silver thin film etching solution compositions were prepared by including the respective components in the amounts described in table 1 below. Etch stop (Etch stop) refers to an Etch stop phenomenon that does not further proceed with etching when the conditions of the etchant composition are changed, and is a parameter that can predict that the value of side etching (side edch) does not increase before SEM (scanning electron microscope) measurement is performed.
The etching stop index of the present invention is (inorganic acid + initiator)/(organic acid + water), the preferable range of the etching stop index is 0.05 to 0.35, the etching stop index is an index of the ratio of the content of inorganic acid and initiator for accelerating the etching rate (Etch rate) to the organic acid for chelating metals, and it can be predicted in advance whether the S/E increases due to the result based on the ratio.
[ Table 1]
(unit: wt%)
Figure BDA0001797006340000081
Experimental example 1 Performance test of silver etchant composition
An ITO/Ag/ITO triple film was formed on a substrate, and an etching process was performed using a jet etching type experimental facility (model name: ETCHER (TFT), SEMES). The silver etchant compositions of examples 1 to 7 and comparative examples 1 to 3 were added to the experimental apparatus, respectively, and the temperature was set to 40 ℃, and then the temperature was raised, and then when the temperature reached 40 ± 0.1 ℃, the etching process of the ITO/Ag/ITO triple film was performed. The total etching time was set to 60 seconds. In the experiment, after the initial time (0 time) of the silver etchant composition was used for evaluation, the same silver etchant composition was used for re-evaluation after 12 hours and 24 hours, respectively.
1. Measurement of silver residue
The silver etchant compositions of examples 1 to 7 and comparative examples 1 to 3 were added to a spray etching type experimental facility (model name: ETCHER (TFT), SEMES Co., Ltd.), and the temperature was set to 40 ℃ and then increased, and then the etching process of the test piece was performed when the temperature reached 40. + -. 0.1 ℃. The total etching time was set to 60 seconds.
After the substrate was placed in the experimental apparatus, spraying was started, and when the etching time of 60 seconds had elapsed, the substrate was taken out and washed with deionized water, and then dried by a hot air drying device, and the photoresist was removed by a photoresist stripper (PR stripper). The residue, which is a phenomenon that silver (Ag) remains without being etched in a portion not covered with the photoresist, was measured by an electron scanning microscope (SEM; model name: SU-8010, manufactured by hitachi) after the cleaning and drying, and evaluated by the following criteria, and the results are shown in the following table 2.
< evaluation criteria for residue measurement >
O: good (no residue generation)
X: failure [ occurrence of residue ]
2. Measurement of silver reabsorption
The silver etchant compositions of examples 1 to 7 and comparative examples 1 to 3 were added to a spray etching type experimental facility (model name: ETCHER (TFT), SEMES Co., Ltd.), and the temperature was set to 40 ℃ and then increased, and then the etching process of the test piece was performed when the temperature reached 40. + -. 0.1 ℃. The total etching time was set to 60 seconds.
After the substrate was placed in the test apparatus, the substrate was taken out and washed with deionized water when the etching time of 60 seconds had elapsed, and then dried by a hot air drying apparatus. The substrate was cut after cleaning and drying and the cross section was measured using a scanning electron microscope (SEM; model name: SU-8010, manufactured by Hitachi Co.). The number of Ag adsorbed on the upper Ti of Ti/Al/Ti of the S/D portion was measured and evaluated by the following criteria, and the results are shown in table 2 below.
< evaluation criteria for silver Re-adsorption >
O: good (less than 50)
X: failure [ more than 50 ]
3. Measuring etch rate EPD
The etching rate EPD was measured by a timer for a time from the time when the substrate was exposed to the chemical agent to the time when the metal portion of the substrate was etched and disappeared, and the results are shown in table 2 below.
4. Measuring Side Etch (Side Etch)
The substrate was cut after cleaning and drying and the cross section was measured using a scanning electron microscope (SEM; model name: SU-8010, manufactured by Hitachi Co.). At this time, the distance from the patterned PR end to the etched metal end was measured, and the results are shown in table 2 below.
[ Table 2]
Figure BDA0001797006340000101
When the examples of the present invention and the comparative examples were examined, the phenomenon that the etching Time (Etch Time) increases as the S/E increases appears in the composition without departing from the content range, and it is understood that the etching stop index derived in the following manner deviates from 0.05 to 0.35.
Etch stop index ═ inorganic acid + initiator)/(organic acid + water)
In addition, it was confirmed that the etching solution composition of the present invention has an excellent effect as an etching solution composition as a side etching is reduced by silver (Ag) residue, re-adsorption of silver (Ag), or an appropriate etching rate.

Claims (11)

1. A silver thin film etching solution composition comprising an organic acid, an inorganic acid, an etching initiator and water, and having an etch stop index of 0.05 to 0.35,
wherein the silver thin film etching solution composition is capable of simultaneously etching a multilayer film composed of a single layer film composed of silver or a silver alloy and an indium oxide film,
wherein the organic acid is contained in an amount of 40 to 65 wt% with respect to the total weight of the silver thin film etching solution composition,
wherein the organic acid comprises acetic acid and citric acid,
wherein the etch stop index is calculated according to the following formula:
etch stop index ═ content of inorganic acid + content of etching initiator)/(content of organic acid + content of water).
2. The silver thin film etching solution composition according to claim 1,
the silver thin film etching solution composition comprises 40-65 wt% of organic acid, 5-10 wt% of inorganic acid, 1-15 wt% of etching initiator and water for making the total weight of the composition 100 wt% relative to the total weight of the silver thin film etching solution composition.
3. The silver thin film etching solution composition according to claim 1,
the inorganic acid includes one or more selected from the group consisting of nitric acid, sulfuric acid, and hydrochloric acid.
4. The silver thin film etching solution composition according to claim 1,
the etching initiator includes one or more selected from the group consisting of a peroxide initiator, an alkali metal initiator, and a transition metal initiator.
5. The silver thin film etching solution composition according to claim 4,
the peroxide initiator comprises one or more selected from the group consisting of sodium persulfate, ammonium persulfate, potassium monopersulfate complex salt, and oxalic acid.
6. The silver thin film etching solution composition according to claim 4,
the alkali metal initiator includes one or more selected from the group consisting of sodium nitrate, potassium nitrate, calcium nitrate, sodium sulfate, potassium sulfate, calcium sulfate, sodium chloride, calcium chloride, and potassium chloride.
7. The silver thin film etching solution composition according to claim 4,
the transition metal initiator includes one or more selected from the group consisting of ferrous nitrate, ferric nitrate, ferrous sulfate, and ferric sulfate.
8. The silver thin film etching solution composition according to claim 1,
the indium oxide film is one or more selected from the group consisting of indium tin oxide, indium zinc oxide, indium tin zinc oxide, and indium gallium zinc oxide.
9. The silver thin film etching solution composition according to claim 1,
the multilayer film composed of the single layer film and the indium oxide film is an indium oxide film/silver, an indium oxide film/silver alloy, an indium oxide film/silver/indium oxide film, or an indium oxide film/silver alloy/indium oxide film.
10. An etching method comprising the steps of:
forming a multilayer film composed of a single-layer film composed of silver or a silver alloy and an indium oxide film on a substrate;
selectively leaving a photoreactive material on a multilayer film composed of the single layer film composed of silver or a silver alloy and an indium oxide film; and
a multilayer film composed of the single-layer film composed of silver or a silver alloy and an indium oxide film is etched using the composition described in claim 1.
11. A method of forming a metal pattern, comprising the steps of:
forming a multilayer film composed of a single-layer film composed of silver or a silver alloy and an indium oxide film; and
a multilayer film composed of the single-layer film composed of silver or a silver alloy and an indium oxide film is etched using the composition described in claim 1.
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