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CN113652693A - Silver thin film etching liquid composition, etching method using the same and metal pattern forming method - Google Patents

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

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CN113652693A
CN113652693A CN202110400750.8A CN202110400750A CN113652693A CN 113652693 A CN113652693 A CN 113652693A CN 202110400750 A CN202110400750 A CN 202110400750A CN 113652693 A CN113652693 A CN 113652693A
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thin film
silver
acid
etching
silver thin
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CN113652693B (en
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南基龙
尹暎晋
李昔准
李原昊
权五柄
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Dongwoo Fine Chem Co Ltd
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    • 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
    • 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment 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
    • H01L21/3205Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/32051Deposition of metallic or metal-silicide layers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment 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
    • H01L21/3205Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321After treatment
    • H01L21/3213Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134Physical 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

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  • General Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • ing And Chemical Polishing (AREA)
  • Weting (AREA)

Abstract

The present invention relates to a silver thin film etching solution composition, an etching method using the same, and a method of forming a metal pattern, wherein the silver thin film etching solution composition comprises: (A) nitric acid; (B) an alkylsulfonic acid having 1 to 3 carbon atoms; (C) organic acids other than alkylsulfonic acids having 1 to 3 carbon atoms; (D) a sulfate salt; (E) a ternary metal salt containing iron; and (F) water.

Description

Silver thin 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, a method for etching using the same, and a method for forming a metal pattern.
Background
A flat panel display apparatus such as an OLED tends to be rapidly applied to a small display market such as a portable device and also to a large display such as a TV in recent years because its device itself emits light and can be driven also at a low voltage.
On the other hand, for wirings of an OLED or an LCD, a reflective plate, an electrode of a color filter, and the like, a metal thin film containing aluminum (Al) has been conventionally used, but recently, a silver (Ag: resistivity of about 1.59 μ Ω cm) film, a silver alloy, or a multilayer film including the same, which has lower resistivity and higher luminance than a metal such as aluminum, has been started to be used.
For example, the wiring and/or the pattern is formed by etching a silver thin film in a silver film, a silver alloy, or a multilayer film including the same using the etching liquid composition.
However, when the silver thin film is etched using the existing etching solution, since silver (Ag) is excessively etched or is not uniformly etched, a phenomenon of warping or peeling of the wiring occurs, and a defect occurs in a side profile of the wiring. In addition, when the silver thin film etching is performed using the silver etchant composition, there occurs a problem in that etched silver particles are again adsorbed on the metal film of the exposed S/D portion within the substrate. At this time, there is a problem of residue caused by re-adsorption, that is, a problem that foreign substances may cause process defects.
In this regard, korean laid-open patent publication No. 10-1391603 discloses a related art of an etching solution for silver-containing patterns, which contains a sulfate-based compound as a main oxidizer, and also contains nitric acid, oxalic acid, acetic acid, and an azole-based compound, and can selectively etch silver or an alloy film containing silver. However, the etching solution disclosed in this patent document does not cause an Etch Stop (Etch Stop) phenomenon, and therefore has the following problems: with the increase of the Etching Time (Etching Time), not only was the undercut (Side Etch) continued to increase and the wiring bite phenomenon occurred, but also, when the process quantity evaluation was performed, re-adsorption of silver was largely caused due to the performance degradation.
[ Prior art documents ]
[ patent document ]
(patent document 1) Korean patent laid-open publication No. 10-1391603
Disclosure of Invention
Technical problem
The present invention is intended to improve the problems of the prior art described above, and an object thereof is to provide a silver thin film etching solution composition which exhibits excellent etching characteristics and etching uniformity when etching a single-layer film made of silver (Ag) or a silver alloy and a multilayer film composed of the single-layer film and a transparent conductive film.
Further, the present invention is directed to an etching method using the silver thin film etchant composition and a method of forming a metal pattern.
Technical scheme
The invention provides a silver film etching solution composition, which comprises: (A) nitric acid; (B) an alkylsulfonic acid having 1 to 3 carbon atoms; (C) organic acids other than alkylsulfonic acids having 1 to 3 carbon atoms; (D) a sulfate salt; (E) a ternary metal salt containing iron; and (F) water.
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.
Advantageous effects
When the silver thin film etching solution composition of the present invention is used, excessive etching of the silver thin film is prevented by an etching stop phenomenon at the time of etching the silver thin film, so that the amount of undercut can be reduced, and thus not only can be easily applied to the formation of fine patterns, but also an effect of remarkably improving problems of silver residue and silver re-adsorption without occurrence of a local excessive etching phenomenon of some wirings, such as a mouse bite phenomenon, can be provided.
In addition, the silver thin film etching solution composition of the present invention simultaneously etches a single layer film made of silver (Ag) or a silver alloy and an etched film of a multi-layer film composed of the single layer film and a transparent conductive film, thereby providing an effect of improving etching efficiency. In addition, the silver thin film etchant composition of the present invention maintains etching performance even when the number of processes is increased, and thus can provide excellent etching uniformity.
Detailed Description
The present invention relates to a silver thin film etching liquid composition, an etching method using the same, and a method of forming a metal pattern, wherein the silver thin film etching liquid composition comprises nitric acid, an alkylsulfonic acid having 1 to 3 carbon atoms, an organic acid other than the alkylsulfonic acid having 1 to 3 carbon atoms, a sulfate, a ternary metal salt containing iron, and water.
The silver thin film etching solution composition of the present invention forms relatively small lateral etching by preventing over-etching of a silver thin film through an etching stop phenomenon when etching the silver thin film by containing an iron-containing ternary metal salt as a component, and thus can be easily applied to the formation of fine patterns, and can provide an effect of remarkably improving silver residue and silver re-adsorption and the like without occurrence of a partial over-etching phenomenon of some wirings, such as a mouse-bite phenomenon. In addition, even when the number of processes is large due to a long-term etching process, the effect of preventing re-adsorption of silver can be maintained excellently without generating residue, and thus excellent etching uniformity can be provided.
In the present invention, the silver thin film includes a single layer film made of silver (Ag) or a silver alloy and a multi-layer film composed of the single layer film and a transparent conductive film, and the silver thin film etchant composition of the present invention is capable of simultaneously etching the single layer film made of silver (Ag) or a silver alloy and the multi-layer film formed of the single layer film and the transparent conductive film.
The silver alloy may include an alloy form containing silver as a main component and further containing other metals such as Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W, Pa, and Ti, and a nitride, silicide, carbide, oxide, and the like of silver, but is not limited thereto.
The transparent conductive film may include at least one selected from the group consisting of indium oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), Indium Tin Zinc Oxide (ITZO), and Indium Gallium Zinc Oxide (IGZO).
The multilayer film may include a transparent conductive film/silver, a transparent conductive film/silver alloy, a transparent conductive film/silver/transparent conductive film, or a transparent conductive film/silver alloy/transparent conductive film.
The silver thin film etching solution composition, the etching method using the same, and the method of forming a metal pattern of the present invention may be used to form an OLED TFT array substrate for a reflective film, trace (trace) wiring or nanowire (nanowire) wiring for a touch screen panel, but are not limited thereto, and may be used for electronic component materials including single-layer films and multi-layer films.
Hereinafter, components contained in the silver thin film etching liquid composition of the present invention will be described.
< silver thin film etching solution composition >
The silver thin film etching solution composition of the present invention comprises (a) nitric acid, (B) an alkylsulfonic acid having 1 to 3 carbon atoms, (C) an organic acid other than the alkylsulfonic acid having 1 to 3 carbon atoms, (D) a sulfate salt, and (E) an iron-containing ternary metal salt, and may further comprise (F) water as a solvent.
(A) Nitric acid
The nitric acid contained in the silver thin film etching solution composition of the present invention is used as an oxidizing agent for oxidizing a silver thin film and a transparent conductive film.
In an embodiment, the nitric acid may be present in an amount of 8 wt% to 15 wt%, based on the total weight of the composition. When the silver thin film etching solution composition of the present invention contains nitric acid within the above-mentioned content range, the etching rate is easily controlled, thereby enabling uniform etching of the silver thin film and the transparent conductive film.
(B) Alkylsulfonic acids having 1 to 3 carbon atoms
The alkylsulfonic acid contained in the silver thin film etching solution composition of the present invention can be used for etching a silver thin film and a transparent conductive film oxidized by nitric acid.
In the present invention, the alkylsulfonic acid preferably has 1 to 3 carbon atoms. The alkylsulfonic acid having 1 to 3 carbon atoms may be, for example, methanesulfonic acid, ethanesulfonic acid or propanesulfonic acid, preferably methanesulfonic acid.
The content of the alkylsulfonic acid may be 3 to 8% by weight, based on the total weight of the composition. When the silver thin film etching solution composition of the present invention contains the alkylsulfonic acid having 1 to 3 carbon atoms within the above content range, the etching rate to the silver thin film and the etching rate to the transparent conductive film are easily controlled, and defects caused by the occurrence of silver residues and silver re-adsorption can be prevented.
(C) Organic acids other than alkylsulfonic acids having 1 to 3 carbon atoms
The organic acid other than the alkylsulfonic acid having 1 to 3 carbon atoms contained in the silver thin film etching liquid composition of the present invention can be used for etching a silver thin film oxidized by nitric acid as an etchant for the silver thin film.
The organic acid may include, for example, at least one selected from the group consisting of acetic acid, citric acid, glycolic acid, malonic acid, lactic acid and tartaric acid, preferably at least two. Most preferably, acetic acid and citric acid may be included.
The content of the organic acid other than the alkylsulfonic acid having 1 to 3 carbon atoms may be 30 to 55% by weight, preferably 40 to 50% by weight, based on the total weight of the composition. When the organic acid is included in the silver thin film etching solution composition of the present invention within the above-mentioned content range, the etching rate of the silver thin film is easily controlled, so that defects due to the occurrence of silver residues and re-adsorption of silver can be prevented.
(D) Sulfates of sulfuric acid
The sulfate contained in the silver thin film etching solution composition of the present invention can be used as an etchant for a transparent conductive film to etch the transparent conductive film.
In addition, the sulfate may function to generate an etch stop phenomenon for the silver thin film, and thus can prevent an increase in the undercut even if the etching time is increased in the etching process.
Therefore, the silver thin film etching solution composition of the present invention can control the occurrence of the etch stop phenomenon by including the sulfate, thereby controlling the etching rate, thereby enabling to adjust the undercut.
The sulfate may be present in an amount of 10 to 25 wt% based on the total weight of the composition.
The sulfate may include at least one selected from the group consisting of potassium hydrogen sulfate, sodium hydrogen sulfate, and ammonium hydrogen sulfate.
When the sulfate is contained in the silver thin film etching solution composition of the present invention within the above-mentioned content range, it is easy to control the etching rate, that is, to control the etching time in the etching process, and the etching stop phenomenon is regularly generated, so that the silver thin film and the transparent conductive film can be uniformly etched.
(E) Ternary metal salt containing iron
In the present invention, the iron-containing ternary metal salt means a compound containing three different ions.
For example, the iron-containing ternary metal salt may be cationic-iron (Fe)3+) Compounds which exist in the form of anions and can be represented as C-Fe-A (cations-Fe-anions). Wherein the cation may be Fe3+Any one of the other cations except the metal ion of (a).
In one embodiment, the iron-containing ternary metal salt of the present invention comprises Fe3+And two ions (cation and anion) different from each other.
The ternary metal salt containing iron contained in the silver thin film etching solution composition of the present invention is used as an oxidizer for the silver thin film, and the effect of the auxiliary oxidizer with nitric acid can be used to prevent defects caused by the occurrence of silver residues and silver re-adsorption.
In addition, it is possible to solve the problems that occur when an etching solution composition containing a silver thin film oxidizer such as a metal (e.g., copper) and a metal salt (e.g., iron nitrate) is used.
For example, when the existing etching liquid composition is used, the etching liquid penetrates into pinholes (Pin holes) existing due to uneven film formation of an upper indium oxide film and impurities such as dust, thereby causing local over-etching, resulting in a mouse-biting phenomenon in which wiring shows a shape like mouse-biting after patterning with the etching liquid composition, but the silver thin film etching liquid composition according to the present invention effectively suppresses the occurrence of the mouse-biting phenomenon, which is one of the local over-etching phenomena occurring during patterning of a silver thin film with an etching liquid, by using an iron-containing ternary metal salt instead of a metal/metal salt such as copper, ferric nitrate.
Specifically, the iron-containing ternary metal salt plays a role in reducing the partial over-etching rate of the metal/metal salt and the silver thin film or reducing the speed of the etching solution penetrating into the pinholes of the upper indium oxide film through the extra cations compared with the existing iron and iron-containing binary metal salts, so that the rat bite phenomenon can be prevented. Therefore, there is an advantage in that a uniform pattern can be formed without causing a mouse-biting phenomenon which may eventually cause a defect of a product.
In one embodiment, the cation of the iron-containing ternary metal salt may comprise one of ammonium, sodium and potassium, preferably an ammonium ion. In addition, the anion of the iron-containing ternary metal salt may include one of sulfate, citrate, oxalate, ethylenediaminetetraacetic acid and oxalate, preferably sulfate.
For example, the iron-containing ternary metal salt included in the silver thin film etchant composition of the present invention may include, but is not limited to, ammonium iron sulfate, ammonium iron citrate, ammonium iron oxalate, potassium iron oxalate, sodium iron oxalate, and the like.
The iron-containing ternary metal salt may include at least one of the above compounds, preferably at least one of ferric ammonium sulfate and ferric ammonium citrate.
In one embodiment, the iron-containing ternary metal salt may be included in the silver thin film etching solution composition of the present invention in an amount of 0.01 wt% to 0.1 wt% with respect to the total weight of the composition. When the content of the iron-containing ternary metal salt is within the above content range, defects due to the occurrence of silver residues and silver re-absorption can be prevented, and a local over-etching phenomenon (mouse-bite phenomenon) of some wirings due to the use of the metal salt does not occur.
(F) Water (W)
The water contained in the silver thin film etching solution composition of the present invention may be deionized water used for a semiconductor process, and preferably deionized water of 18M Ω cm or more may be used.
In the present invention, water may be contained in a balance, wherein the balance refers to a balance such that the total weight of the composition further containing the essential ingredients of the present invention and other ingredients becomes 100% by weight.
For example, the water content in the present invention may be 20 to 38% by weight, based on the total weight of the composition.
In one embodiment, the silver thin film etchant composition of the present invention preferably does not contain phosphoric acid that causes re-adsorption of silver residues and silver.
The present invention can exhibit excellent etching characteristics and etching uniformity when etching a single-layer film made of silver (Ag) or a silver alloy and a multi-layer film composed of the single-layer film and a transparent conductive film.
< etching method Using silver thin film etching solution composition >
In addition, the present invention provides an etching method using the silver thin film etchant composition according to the present invention. The etching method of the present invention may form a pattern according to a known metal etching method, in addition to using the silver thin film etching solution composition of the present invention.
For example, the etching method may include: i) forming a single-layer film made of silver or a silver alloy or a multilayer film composed of the single-layer film and a transparent conductive film on a substrate; ii) selectively retaining the photoreactive material on the single layer film or the multilayer film; and iii) etching the monolayer film or the multilayer film using the silver thin film etching solution composition according to the present invention.
< method for Forming Metal Pattern Using silver thin film etching solution composition >
In addition, the present invention provides a method of forming a metal pattern using the silver thin film etchant composition according to the present invention. The method for forming a metal pattern of the present invention may form a pattern according to a known metal pattern forming method, in addition to using the silver thin film etchant composition of the present invention.
For example, the method of forming the metal pattern may include: i) forming a single-layer film made of silver or a silver alloy or a multilayer film composed of the single-layer film and a transparent conductive film on a substrate; and ii) etching the monolayer film or the multilayer film using the silver thin film etching solution composition according to the present invention.
Hereinafter, the present invention will be described in more detail by examples. However, the following examples are only for illustrating the present invention in more detail, and the scope of the present invention is not limited by the following examples. The scope of the present invention is defined by the appended claims, and particularly, includes all modifications within the meaning and scope equivalent to the recited claims. In the following examples and comparative examples, "%" and "part(s)" representing the content are based on weight unless otherwise specified.
Examples and comparative examples: preparation of silver thin film etching solution composition
The silver thin film etching solution compositions of examples 1 to 3 and comparative examples 1 to 4 were prepared according to the compositions shown in table 1 below, and such that the balance of water was included to make the total weight of the composition 100 wt% (unit: wt%).
[ Table 1]
Figure BDA0003020201710000081
B1: methanesulfonic acid
C1: acetic acid
C2: citric acid
D1: sodium hydrogen sulfate
D2: ammonium hydrogen sulfate
E1: ammonium-Fe-sulfate (ammonium iron sulfate)
E2: ammonium-Fe-citrate (ferric ammonium citrate)
E' 1: fe-nitrate (ferric nitrate)
E' 2: copper (Cu)
Examples of the experiments
1. New etching solution and old etching solution
The state of the silver thin film etching liquid compositions of examples 1 to 3 and comparative examples 1 to 4 just after preparation was referred to as a new etching liquid, and the state (treatment quantity evaluation) after 1000ppm of silver powder was artificially dissolved in order to assume that the etching liquids of examples and comparative examples have been subjected to an etching process for a long time was referred to as an old etching liquid.
Etching characteristics were evaluated by the following methods 2 to 5 using a new etching solution and an old etching solution, respectively.
2. Measurement of lateral erosion
After an ITO/silver/ITO three-layer film was formed on a substrate, a photoresist was patterned on the three-layer film.
The silver thin film etching solution compositions of examples 1 to 3 and comparative examples 1 to 4 were respectively put into a spray type etching method experimental facility (model: etcher (tft), SEMES corporation), and the temperature was raised after setting the temperature at 40 ℃, and an etching process was performed on the etching sample when the temperature reached 40 ± 0.1 ℃. Further, 50% and 100% over-etching was performed from the time when etching of the ITO/silver/ITO triple-layer film was finished, and then the distance from the edge of the patterned photoresist to the etched silver (Ag) film was measured using a scanning electron microscope (SEM; model: SU-8010, HITACHI). (the level of undercut currently satisfactory to the customer is 0.3 μm or less, and if it exceeds 0.3. mu.m, it is regarded as a fail (spec.out))
3. silver/ITO residue measurement
After an ITO/silver/ITO three-layer film is formed on a substrate, a photoresist is patterned on the three-layer film. The silver thin film etching solution compositions of examples 1 to 3 and comparative examples 1 to 4 were respectively put into a spray type etching method experimental facility (model: etcher (tft), SEMES corporation), and the temperature was raised after setting the temperature at 40 ℃, and an etching process was performed on the etching sample when the temperature reached 40 ± 0.1 ℃. The total etching time was implemented as 85 seconds. The substrate was put in and sprayed, and when the etching time exceeded 85 seconds, it was taken out, washed with deionized water, dried with a hot air drying device, and the photoresist was removed with a photoresist stripper (PR stripper). After cleaning and drying, an electron scanning microscope (SEM; model: SU-8010, manufactured by HITACHI) was used to measure a residue, which is a phenomenon in which silver (Ag) remained without being etched exists in a portion not covered with the photoresist. The evaluation was carried out according to the following criteria, and the results are shown in Table 2.
< evaluation criteria for residue measurement >
Good: [ absence of Ag and ITO residues ]
Poor: [ production of Ag or ITO residue ]
4. Re-adsorption of silver
After an ITO/silver/ITO three-layer film is formed on a substrate, a photoresist is patterned on the three-layer film.
The silver thin film etching solution compositions of examples 1 to 3 and comparative examples 1 to 4 were respectively put into a spray type etching method experimental facility (model: etcher (tft), SEMES corporation), and the temperature was raised after setting the temperature at 40 ℃, and an etching process was performed on the etching sample when the temperature reached 40 ± 0.1 ℃. The total etching time was implemented as 85 seconds. The substrate was put in and sprayed, and when the etching time exceeded 85 seconds, it was taken out, washed with deionized water, and dried using a hot air drying apparatus. After cleaning and drying, the substrate was cut and measured using a scanning electron microscope (SEM; model: SU-8010, manufactured by HITACHI corporation). The number of silver particles adsorbed to the upper Ti layer in the Ti/Al/Ti triple layer film of the source/drain portions exposed on the substrate due to the etching process was measured and evaluated according to the following criteria, and the results thereof are shown in table 2.
< evaluation Standard for silver Re-adsorption >
Good: [ the amount of re-adsorption of silver does not exceed 10]
Poor: [ silver reabsorption quantity exceeds 10]
5. Mouse bite phenomenon (local over-etching of wiring)
The silver thin film etching solution compositions of examples 1 to 3 and comparative examples 1 to 4 were respectively put into a spray type etching type experimental device (model: 5.5ETCHER, Prowet corporation), the temperature was raised after setting the temperature to 40 ℃, and the etching process was performed on the sample when the temperature reached 40 ± 0.1 ℃. The total etching time was implemented as 100 seconds. The substrate was put in and sprayed, and when the etching time exceeded 100 seconds, it was taken out, washed with deionized water, dried using a hot air drying device, and then the photoresist was removed using a photoresist stripper (PR stripper). After cleaning and drying, an experiment was performed using a scanning electron microscope (SEM; model: SU-8010, manufactured by HITACHI) in a method of performing analysis after etching, and evaluation was performed according to the following criteria, and the results thereof are shown in Table 2.
[ evaluation criteria for local over-etching (mouse bite) ]
O: excellent (there is no portion where the local wiring width is reduced to a level of 1.5 μm or less)
X: failure (there is a portion where the local wiring width is reduced to a level of 1.5 μm or less)
[ Table 2]
Figure BDA0003020201710000111
Referring to table 2, it can be confirmed that: the silver thin film etchant compositions of examples 1 to 3 had excellent effects in terms of side etching, silver residue/ITO residue, and silver re-adsorption in both the new etchant and the old etchant, and a mouse-biting phenomenon in which the wiring portion was excessively etched did not occur.
On the other hand, in the case of comparative examples 1 to 4, it was confirmed that: not only the silver residue and the re-adsorption of silver, etc., but also the old etching solution composition. In particular, in the case of comparative examples 2 and 3 using an iron-containing binary metal salt instead of the iron-containing ternary metal salt of the present invention and comparative example 4 using a metal, it was confirmed that a rat bite phenomenon occurred or a silver residue/ITO residue defect occurred.
Therefore, when the silver thin film etching solution composition of the present invention was used, since the composition contained the iron-containing ternary metal salt, it was confirmed that: has the effect of reducing the occurrence of local over-etching of the silver thin film and more effectively preventing the generation of Ag residue/ITO residue.

Claims (11)

1. A silver thin film etchant composition comprising: nitric acid; an alkylsulfonic acid having 1 to 3 carbon atoms; organic acids other than alkylsulfonic acids having 1 to 3 carbon atoms; a sulfate salt; a ternary metal salt containing iron; and water.
2. The silver thin film etching solution composition according to claim 1, wherein the alkylsulfonic acid having 1 to 3 carbon atoms is methanesulfonic acid.
3. The silver thin film etching solution composition according to claim 1, wherein the organic acid other than the alkylsulfonic acid having 1 to 3 carbon atoms includes at least one selected from the group consisting of acetic acid, citric acid, glycolic acid, malonic acid, lactic acid and tartaric acid.
4. The silver thin film etching solution composition according to claim 1, wherein the sulfate salt includes at least one selected from the group consisting of potassium bisulfate, sodium bisulfate, and ammonium bisulfate.
5. The silver thin film etching solution composition of claim 1, wherein the iron-containing ternary metal salt is capable of being converted into cation-iron (Fe)3+) -compounds in the form of anions.
6. The silver thin film etchant composition according to claim 5, wherein the cation comprises one of ammonium, sodium and potassium.
7. The silver thin film etching solution composition of claim 5, wherein the anion comprises one of sulfate, citrate, oxalate, ethylenediaminetetraacetic acid, and oxalate.
8. The silver thin film etchant composition according to any one of claims 1 to 5, wherein the iron-containing ternary metal salt includes at least one of ammonium iron sulfate, ammonium iron citrate, ammonium iron oxalate, potassium iron oxalate and sodium iron oxalate.
9. The silver thin film etching solution composition according to claim 1, comprising, based on the total weight of the composition:
8 to 15 weight percent nitric acid;
3 to 8 wt% of an alkyl sulfonic acid having 1 to 3 carbon atoms;
30 to 55% by weight of an organic acid other than an alkylsulfonic acid having 1 to 3 carbon atoms;
10 to 25 wt% of a sulfate salt;
0.01 to 0.1% by weight of an iron-containing ternary metal salt; and
and (3) water.
10. An etching method, comprising:
forming a single-layer film made of silver or a silver alloy or a multilayer film composed of the single-layer film and a transparent conductive film on a substrate;
selectively retaining a photoreactive material on the single layer film or on the multilayer film; and
etching the single layer film or the multi-layer film by using the silver thin film etching solution composition of claim 1.
11. A method of forming a metal pattern, comprising:
forming a single-layer film made of silver or a silver alloy or a multilayer film composed of the single-layer film and a transparent conductive film on a substrate; and
etching the single layer film or the multi-layer film by using the silver thin film etching solution composition of claim 1.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114277373A (en) * 2021-12-28 2022-04-05 江阴江化微电子材料股份有限公司 Long-life silver film etching solution composition and etching process
CN116411278A (en) * 2023-04-12 2023-07-11 上海盛剑微电子有限公司 A kind of etching solution and its preparation method and application

Citations (3)

* 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
CN110284140A (en) * 2018-03-16 2019-09-27 东友精细化工有限公司 The manufacturing method of etchant containing Ag films and the array substrate for display device using it
CN110644003A (en) * 2018-06-26 2020-01-03 东友精细化工有限公司 Silver thin film etching solution composition, etching method using same, and method for forming metal pattern

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101391603B1 (en) 2012-05-22 2014-05-07 솔브레인 주식회사 Echant for silver pattern
KR102599939B1 (en) * 2018-06-26 2023-11-09 동우 화인켐 주식회사 Etchant composition for silver thin layer and ehting method and mehtod for fabrication metal pattern using the same

Patent Citations (3)

* 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
CN110284140A (en) * 2018-03-16 2019-09-27 东友精细化工有限公司 The manufacturing method of etchant containing Ag films and the array substrate for display device using it
CN110644003A (en) * 2018-06-26 2020-01-03 东友精细化工有限公司 Silver thin film etching solution composition, etching method using same, and method for forming metal pattern

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114277373A (en) * 2021-12-28 2022-04-05 江阴江化微电子材料股份有限公司 Long-life silver film etching solution composition and etching process
CN114277373B (en) * 2021-12-28 2023-12-26 江阴江化微电子材料股份有限公司 Silver film etching solution composition with long service life and etching process
CN116411278A (en) * 2023-04-12 2023-07-11 上海盛剑微电子有限公司 A kind of etching solution and its preparation method and application

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