CN109797397B - Silver etchant composition, etching method using the same, and method for forming metal pattern - Google Patents

Silver etchant composition, etching method using the same, and method for forming metal pattern Download PDF

Info

Publication number
CN109797397B
CN109797397B CN201811201730.2A CN201811201730A CN109797397B CN 109797397 B CN109797397 B CN 109797397B CN 201811201730 A CN201811201730 A CN 201811201730A CN 109797397 B CN109797397 B CN 109797397B
Authority
CN
China
Prior art keywords
silver
indium oxide
etching
oxide film
layer film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811201730.2A
Other languages
Chinese (zh)
Other versions
CN109797397A (en
Inventor
金镇成
金宝衡
金兑勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongwoo Fine Chem Co Ltd
Original Assignee
Dongwoo Fine Chem Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongwoo Fine Chem Co Ltd filed Critical Dongwoo Fine Chem Co Ltd
Publication of CN109797397A publication Critical patent/CN109797397A/en
Application granted granted Critical
Publication of CN109797397B publication Critical patent/CN109797397B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-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
    • C23F1/00Etching metallic material by chemical means
    • C23F1/10Etching compositions
    • C23F1/14Aqueous compositions
    • C23F1/16Acidic compositions
    • C23F1/30Acidic compositions for etching other metallic material
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00Etching, surface-brightening or pickling compositions
    • C09K13/04Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/06Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-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
    • C23F1/00Etching metallic material by chemical means
    • C23F1/02Local etching

Landscapes

  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Weting (AREA)
  • ing And Chemical Polishing (AREA)
  • Electroluminescent Light Sources (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

Abstract

The present invention relates to a silver etchant composition comprising 30 to 70 wt% of phosphoric acid, 2 to 9 wt% of nitric acid, 0.1 to 9 wt% of an acetate compound, 0.1 to 10 wt% of ferric nitrate, and the balance of water for making the total weight of the composition 100 wt%, an etching method using the same, and a method of forming a metal pattern.

Description

Silver etchant composition, etching method using the same, and method for forming metal pattern
Technical Field
The present invention relates to a silver etchant composition, an etching method using the same, and a method of forming a metal pattern, and more particularly, to a silver etchant composition including 30 to 70 wt% of phosphoric acid, 2 to 9 wt% of nitric acid, 0.1 to 9 wt% of an acetate compound, 0.1 to 10 wt% of ferric nitrate, and the balance of water to make the total weight of the composition 100 wt%, based on the total weight of the composition.
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 to an insulating substrate such as glass or to a lower substrate such as a semiconductor substrate made of typical amorphous silicon or doped amorphous silicon, and is not easily deposited, and floating (lifting) or Peeling (Peeling) of the 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. 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 a short circuit.
For this reason, studies for improving etching characteristics are actively conducted, and as a representative example, it is proposed in korean laid-open patent No. 10-2008-0110259 to include phosphoric acid, nitric acid, acetic acid, and sodium dihydrogen phosphate (NaH) at specific contents2PO4) And an etchant composition with deionized water. However, there is still a demand for an etching solution composition capable of improving etching characteristics for silver in this technical field, and active research is being conducted in compliance with 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 and Korean published patent No. 10-2008-0110259
Disclosure of Invention
Technical problem
The present invention provides a silver etchant composition for etching a single-layer film made of silver or a silver alloy or a multi-layer film made of the single-layer film and an indium oxide film, which exhibits etching characteristics of excellent etching straightness and uniformity without causing problems of lower wiring loss, residue (for example, silver residue and/or indium oxide film residue) generation and silver re-adsorption, and without causing a problem of discoloration of an etching apparatus.
In addition, the present invention provides an etching method using the silver etchant composition.
In addition, the present invention provides a method of forming a metal pattern using the silver etchant composition.
Means for solving the problems
In order to achieve the above object, the present invention provides a silver etchant composition comprising, relative to the total weight of the composition, 30 to 70 wt% of phosphoric acid, 2 to 9 wt% of nitric acid, 0.1 to 9 wt% of an acetate compound, 0.1 to 10 wt% of ferric nitrate, and the balance water to make the total weight of the composition 100 wt%.
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 multilayer film composed of the single-layer film and an indium oxide film using the silver etchant 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 multilayer film composed of the single-layer film and an indium oxide film using the silver etchant composition.
Effects of the invention
The silver etchant composition of the present invention has the following effects: when a single layer film composed of silver or silver alloy or a multilayer film composed of the single layer film and an indium oxide film is etched, the problem of lower wiring loss, the problem of residue (for example, silver residue and/or indium oxide film residue) generation and the problem of silver re-adsorption are not generated, and the etching characteristics with excellent etching straightness and uniformity are presented, and the problem of discoloration of an etching device is not caused.
Detailed Description
The present invention will be described in more detail below.
The present invention relates to a silver etchant composition comprising, relative to the total weight of the composition, 30 to 70 wt% of phosphoric acid, 2 to 9 wt% of nitric acid, 0.1 to 9 wt% of an acetate compound, 0.1 to 10 wt% of ferric nitrate, and the balance of water to make the total weight of the composition 100 wt%. The present inventors have confirmed that a problem of lower wiring loss, a problem of residue (for example, silver residue and/or indium oxide film residue), and a problem of silver re-adsorption do not occur 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 using the etchant composition as described above, and that the etching characteristics excellent in etching straightness and uniformity are exhibited without causing a problem of discoloration of an etching apparatus, thereby completing the present invention.
The silver etchant 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 etchant 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.
The indium oxide is at least one selected from the group consisting of Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and Indium Gallium Zinc Oxide (IGZO).
Further, the multilayer film may be a multilayer 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 when the silver etchant composition of the present invention is used, the silver etchant composition of the present invention can be effectively used in wet etching without causing problems of lower wiring loss, generation of residue (for example, silver residue and indium oxide film residue), and silver re-adsorption, while exhibiting etching characteristics excellent in etching straightness and uniformity, and without causing a problem of discoloration of an etching apparatus.
Phosphoric acid (H) contained in the silver etchant composition of the present invention3PO4) The main etchant plays a role of inducing a redox reaction with silver (Ag) or a silver alloy and performing wet etching by dissociating an indium oxide film when etching a single layer film or a multilayer film.
The phosphoric acid is contained in an amount of 30 to 70 wt%, preferably 40 to 70 wt%, and more preferably 40 to 60 wt%, relative to the total weight of the silver etchant composition.
In the case where the content of phosphoric acid is less than 30% by weight relative to the total weight of the composition, sufficient etching cannot be achieved due to insufficient etching ability. Further, when a predetermined amount or more of silver (Ag) is dissolved and taken into the etching solution composition due to the progress of the steps, re-adsorption of silver (Ag) or precipitation of silver (Ag) may occur, which may cause short-circuiting in the subsequent steps and may cause a problem.
In the case where the content of phosphoric acid is more than 70% by weight with respect to the total weight of the composition, overetching may occur due to a decrease in the etching rate of the indium oxide film and an excessively high etching rate of silver or a silver alloy, and thus an etching amount may occur that causes a wiring function to be unable to be performed. In addition, in the case of a multilayer film in which an indium oxide film is laminated on silver or a silver alloy, a Tip (Tip) due to a difference in etching rate between silver or a silver alloy and an indium oxide film may occur, causing a problem in a subsequent process.
Nitric acid (HNO) contained in the silver etchant composition of the present invention3) In order to serve as a component assisting the action of the etchant, silver (Ag) or a silver alloy and an indium oxide film are oxidized to perform a wet etching action when etching a single-layer film or a multilayer film.
The nitric acid is contained in an amount of 2 to 9 wt%, preferably 4 to 6 wt%, with respect to the total weight of the silver etchant composition.
When the content of nitric acid is less than 2 wt% with respect to the total weight of the composition, the etching rate of silver or a silver alloy and the indium oxide film is decreased, and thus the etching Uniformity (Uniformity) in the substrate is deteriorated, and the mottling may occur.
When the content of nitric acid is more than 9 wt% based on the total weight of the composition, there is a possibility that the etching rate of the upper and lower indium oxide films is accelerated and overetching of the upper and lower indium oxide films occurs, thereby causing a problem in the subsequent process.
The acetate compound contained in the silver etchant composition of the present invention functions as follows: when wet etching is performed, the etching rate is adjusted with the passage of time, and the residue of the indium oxide film is controlled.
The acetate compound is contained in an amount of 0.1 to 9 wt%, preferably 0.5 to 9 wt%, and more preferably 0.5 to 8 wt%, relative to the total weight of the silver etchant composition.
In the case where the content of the acetate compound is less than 0.1% by weight relative to the total weight of the composition, the etching ability and the ability to adjust the etching rate with the passage of time may be reduced.
In the case where the content of the acetate compound is more than 9% by weight with respect to the total weight of the composition, there is a possibility that the etching rate is excessively hindered by the inhibition of the action of phosphoric acid or nitric acid.
The acetate compound contained in the etching solution of the present invention may be one or more selected from the group consisting of ammonium acetate, sodium acetate and potassium acetate.
The iron nitrate contained in the silver etchant composition of the present invention is a component used as an auxiliary oxidizing agent and an Ag ligand, and plays the following roles in wet etching: reduce the re-adsorption of silver to the film, and adjust the etching rate and control the residue of the indium oxide film in a uniform etching manner.
The iron nitrate is contained in an amount of 0.1 to 10 wt%, preferably 1 to 5 wt%, with respect to the total weight of the silver etchant composition.
In the case where the content of the ferric nitrate is less than 0.1 wt% with respect to the total weight of the composition, there is a possibility that etching Uniformity (Uniformity) within the substrate may be reduced.
In the case where the content of ferric nitrate is more than 10% by weight with respect to the total weight of the composition, it may be difficult to adjust the etching rate due to the increased etching rate, and there may occur a problem of discoloration of an etching apparatus or difficulty in securing the straightness of an etched pattern (in particular, indium oxide film/silver/indium oxide film or indium oxide film/silver alloy/indium oxide film).
The silver etching solution composition simultaneously containing the acetate and the nitrate has the following effects: the residue of the indium oxide film can be controlled even after 24 hours.
As water contained in the silver etchant 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 etchant composition of the present invention may further include one or more of an etching regulator and a pH regulator, which are generally used in the art, in addition to the above-mentioned components.
The etching regulator which can be further contained may be glycolic acid, glutamic acid, glycine, or the like.
The silver etchant composition of the present invention does not contain acetic acid (acetic acid), and therefore, can minimize the loss of wiring over time and can achieve the effect of improving Ag re-adsorption.
The silver etchant composition of the present invention can be used as an etchant for a single-layer film using a silver/silver alloy or a multilayer 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, a TSP (touch screen panel) Trace wiring, and a Flexible nanowire wiring of a display (OLED, LCD, etc.). 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.
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 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 etchant 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 etchant 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 etchant composition>
Examples 1 to 11 and comparative examples 1 to 12
Silver etchant compositions were prepared by mixing the respective components in the amounts shown in table 1 below.
[ Table 1]
(unit: wt%)
Figure BDA0001830174760000081
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 11 and comparative examples 1 to 12 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. Measuring wiring loss
As for the loss of the wiring (or the reflective film), the wiring loss was measured by measuring the single-sided etching distance (S/E, Side Etch). The silver etchant compositions of examples 1 to 11 and comparative examples 1 to 12 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, 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.). As a one-sided etching distance measurement standard, the width from the end of the photoresist to the inside of the photoresist where metal was etched was measured, and the results are shown in table 2 below by evaluating the following standard.
< evaluation criteria for one-sided etching distance measurement >
O: good [ S/E: less than 0.5 μm ]
X: poor [ S/E: 0.5 μm or more ]
2. Re-adsorption of silver
The silver etchant compositions of examples 1 to 11 and comparative examples 1 to 12 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, 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 to 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. Silver residue measurement
The silver etchant compositions of examples 1 to 11 and comparative examples 1 to 12 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, the 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 ]
4. Indium oxide film (ITO) residue measurement
The silver etchant compositions of examples 1 to 11 and comparative examples 1 to 12 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 ITO 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 cleaning and drying, and evaluated by the following criteria, and the results are shown in the following table 3.
< evaluation criteria for residue measurement >
O: good (no residue generation)
X: failure [ occurrence of residue ]
5. Measuring damage (discoloration) of etching equipment
After the etching compositions were charged into the etching equipment, the temperature was set to 40 ℃ and the temperature was raised, and then whether the color of the etching equipment changed or not was evaluated, and the results are shown in table 3 below.
O: good (no damage (discoloration))
X: failure [ occurrence of Damage (discoloration) ]
6. Measuring straightness of an etched pattern
The silver etchant compositions of examples 1 to 11 and comparative examples 1 to 12 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 ITO/Ag/ITO straight advancing property of the portion not covered with the photoresist was measured using an electron scanning microscope (SEM; model name: SU-8010, manufactured by Hitachi Co., Ltd.) after washing and drying, and evaluated using the following criteria, the results of which are shown in the following Table 3.
O: good (straight advancing property less than 0.2 μm)
X: poor (straight forward property of 0.2 μm or more)
[ Table 2]
Figure BDA0001830174760000121
[ Table 3]
Figure BDA0001830174760000131
The etchant composition of the present invention was confirmed to have excellent effects in all of the loss of wiring, re-adsorption of silver (Ag), silver (Ag) residue, ITO residue, damage (discoloration) of devices, and the presence or absence of straight-ahead movement.

Claims (7)

1. A silver etchant composition is provided,
comprising 30 to 70% by weight of phosphoric acid, 2 to 9% by weight of nitric acid, 0.1 to 9% by weight of an acetate compound, 0.1 to 10% by weight of ferric nitrate and the balance water, relative to the total weight of the composition, making the total weight of the composition 100% by weight,
wherein the silver etchant composition does not contain acetic acid.
2. The silver etchant composition according to claim 1,
the acetate compound is one or more selected from the group consisting of ammonium acetate, sodium acetate, and potassium acetate.
3. The silver etchant composition according to claim 1,
the silver etchant composition can simultaneously etch 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.
4. The silver etchant composition according to claim 3,
the indium oxide is one or more selected from the group consisting of indium tin oxide, indium zinc oxide, and indium gallium zinc oxide.
5. The silver etchant composition according to claim 3,
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.
6. 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 multilayer film composed of the single-layer film and an indium oxide film is etched using the composition according to claim 1.
7. 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 multilayer film composed of the single-layer film and an indium oxide film is etched using the composition according to claim 1.
CN201811201730.2A 2017-11-16 2018-10-16 Silver etchant composition, etching method using the same, and method for forming metal pattern Active CN109797397B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020170152915A KR102218937B1 (en) 2017-11-16 2017-11-16 Etchant composition for silver thin layer and ehting method and mehtod for fabrication metal pattern using the same
KR10-2017-0152915 2017-11-16

Publications (2)

Publication Number Publication Date
CN109797397A CN109797397A (en) 2019-05-24
CN109797397B true CN109797397B (en) 2021-05-04

Family

ID=66556207

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811201730.2A Active CN109797397B (en) 2017-11-16 2018-10-16 Silver etchant composition, etching method using the same, and method for forming metal pattern

Country Status (2)

Country Link
KR (1) KR102218937B1 (en)
CN (1) CN109797397B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113637972B (en) * 2020-05-11 2024-03-26 东友精细化工有限公司 Silver thin film etching liquid composition, etching method using the same, and metal pattern forming method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105887091A (en) * 2015-02-16 2016-08-24 东友精细化工有限公司 Etchant Composition For Ag Thin Layer And Method For Fabricating Metal Pattern Using The Same And Method For Fabricating Array Substrate By Using The Same
CN105951101A (en) * 2015-03-09 2016-09-21 东友精细化工有限公司 Etching solution composition for silver-containing film and manufacturing method of an array substrate for display device using the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101323458B1 (en) 2007-06-15 2013-10-29 동우 화인켐 주식회사 Etchant composition for silver

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105887091A (en) * 2015-02-16 2016-08-24 东友精细化工有限公司 Etchant Composition For Ag Thin Layer And Method For Fabricating Metal Pattern Using The Same And Method For Fabricating Array Substrate By Using The Same
CN105951101A (en) * 2015-03-09 2016-09-21 东友精细化工有限公司 Etching solution composition for silver-containing film and manufacturing method of an array substrate for display device using the same

Also Published As

Publication number Publication date
CN109797397A (en) 2019-05-24
KR20190055980A (en) 2019-05-24
KR102218937B1 (en) 2021-02-23

Similar Documents

Publication Publication Date Title
KR102546803B1 (en) Etching solution composition for silver-containing layer and an display substrate using the same
KR20160108944A (en) Etching solution composition for silver-containing layer and manufacturing method of an array substrate for display device using the same
CN108930038B (en) Silver thin film etching solution composition, etching method and metal pattern forming method
KR102245565B1 (en) Etching solution composition for silver layer and an display substrate using the same
CN110644003B (en) Silver thin film etching solution composition, etching method using same, and method for forming metal pattern
TWI636157B (en) Etching solution composition for silver layer and display substrate using the same
CN109750292B (en) Silver etchant composition, etching method using the same, and method for forming metal pattern
TWI679308B (en) Etching solution composition for silver and display substrate using the same
CN109797396B (en) Silver film etching liquid composition, etching method using the same and metal pattern forming method
CN105755472B (en) Silver etchant composition and display substrate using the same
CN109797397B (en) Silver etchant composition, etching method using the same, and method for forming metal pattern
CN110158088B (en) Silver film etching liquid composition, etching method using the same and metal pattern forming method
KR102639626B1 (en) An etchant composition for silver thin layer and an ehting method and a mehtod for fabrication metal pattern using the same
CN108385109B (en) Etching solution composition and method for manufacturing array substrate for display device using same
KR20190112622A (en) Etching solution composition for silver-containing layer, an array substrate for display device using the same and manufacturing method for the array substrate for display device
KR20190109215A (en) An etching solution composition for silver-containing layer and a manufacturing method for an array substrate for display device using the same
CN110359050B (en) Silver-containing thin film etching solution composition, array substrate for display device manufactured by using same, and manufacturing method thereof
KR102368371B1 (en) Etchant composition for silver thin layer and ehting method and mehtod for fabrication metal pattern using the same
KR20190057018A (en) Etchant composition for silver thin layer and ehting method and mehtod for fabrication metal pattern using the same
CN111172541B (en) Silver thin film etching solution composition, etching method and metal pattern forming method
CN111155092B (en) Silver thin film etching solution composition, etching method and metal pattern forming method
CN110295367B (en) Silver film etching liquid composition, etching method using the same and metal pattern forming method
KR20230118059A (en) Etching solution composition for silver-containing layer and manufacturing method for an array substrate for display device using the same
KR102513168B1 (en) Etching solution composition for silver-containing layer and an display substrate using the same
KR20190111689A (en) Etching solution composition for silver-containing layer and manufacturing method for an array substrate for display device using the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant