CN111172541B - Silver thin film etching solution composition, etching method and metal pattern forming method - Google Patents
Silver thin film etching solution composition, etching method and metal pattern forming method Download PDFInfo
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- CN111172541B CN111172541B CN201911099894.3A CN201911099894A CN111172541B CN 111172541 B CN111172541 B CN 111172541B CN 201911099894 A CN201911099894 A CN 201911099894A CN 111172541 B CN111172541 B CN 111172541B
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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
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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
- C23F1/02—Local etching
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
Abstract
The invention provides a silver thin film etching solution composition, an etching method and a method for forming a metal pattern, wherein the silver thin film etching solution composition comprises: (A) nitric acid; (B-1) an alkylsulfonic acid; (B-2) an organic acid other than an alkylsulfonic acid; (C) one or more of a metal, a metal salt and sulfuric acid; (D) a sulfate salt; and (E) water. The present invention provides an effect of remarkably improving the residue (for example, silver residue and/or transparent conductive film residue) and the problem of silver re-adsorption.
Description
Technical Field
The present invention relates to a silver thin film etching solution composition, an etching method using the same, and a method for forming a metal pattern.
Background
As the information age is really stepped into, the field of displays that process and display a large amount of information is rapidly developing, and a large number of flat panel displays have been developed and are receiving attention.
Examples of such flat Panel Display devices include Liquid crystal Display devices (LCDs), Plasma Display devices (PDPs), Field Emission Display devices (FEDs), electroluminescent Display devices (ELDs), and Organic Light Emitting Displays (OLEDs), and such flat Panel Display devices are used not only in the Field of home appliances such as televisions and video recorders, but also in computers such as notebooks, mobile phones, and the like for various applications. These flat panel display devices are rapidly replacing conventional Cathode Ray Tubes (CRT) because of their excellent performance such as reduction in thickness and weight and reduction in power consumption.
In particular, since the OLED itself emits light and can be driven even at a low voltage, it has been rapidly applied to the market of small displays such as portable devices in recent years. In addition, the current state of the OLED is spanning from a small display to commercialization of a large TV.
In addition, although aluminum (Al) reflectors have been mainly used as products in the past, in order to achieve low power consumption by improving brightness, a search has been made for a metal whose material has been changed to a metal with a higher reflectance. For this reason, it is desired to apply a silver (Ag: resistivity about 1.59 μ Ω cm) film, a silver alloy or a multilayer film including the same, which has lower resistivity and higher brightness than metals applied in a flat panel display device, to electrodes of color filters, LCD or OLED wirings and reflective plates, to realize large-scale, high resolution, low power consumption, and the like of the flat panel display device, and thus it is required to develop an etching solution for application of the material.
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 is not easily vapor-deposited, and tends to induce lift-off (Peeling) or Peeling (Peeling) of wiring. In the case of depositing a silver (Ag) conductive layer on a substrate, an etching solution is used for patterning the conductive layer. When a conventional etching solution is used as such an etching solution, silver (Ag) is excessively etched or unevenly etched, whereby a phenomenon of peeling or peeling of the wiring occurs, and a defect occurs in a side profile of the wiring.
In addition, LOW Skew (LOW Skew) presentation for realizing high resolution has difficulty in terms of process.
In particular, silver (Ag) is a metal which is easily reduced, and etching can be performed without inducing a residue only when the etching rate is high, and in this case, since the etching rate is high and a difference in etching rate does not occur between the upper and lower portions, it is difficult to form a taper angle (taper angle) after etching, and it is difficult to ensure straightness of an etching pattern, there are many limitations in forming wiring and a pattern. Further, when a silver thin film is etched using the silver etchant composition, there is a problem that the silver particles after etching are re-adsorbed to the metal film of the S/D portion exposed in the substrate, and in this case, there is a problem in that a residue problem due to re-adsorption, that is, a process failure due to foreign matter may be caused.
In connection with this, korean laid-open patent No. 10-2008-0110435 and the like have mainly developed a phosphoric acid-based silver etchant composition that requires the use of phosphoric acid as a main oxidant, but has a problem of generating a phosphoric acid-based etchant composition such as damage of a lower film due to phosphoric acid. Therefore, it is actually necessary to develop an etching solution composition having excellent etching characteristics without including silver phosphate, and particularly, it is necessary to develop a non-phosphate silver etching solution composition capable of completely solving the problems of re-adsorption of residue and silver, which are major problems in the art, and the performance degradation of the etching solution composition due to the number of processed sheets.
Documents of the prior art
Patent document
Patent document 1: korean laid-open patent No. 10-2008-0110435
Disclosure of Invention
Problems to be solved
In order to solve the above problems of the prior art, an object of the present invention is to provide a silver thin film etching solution composition for etching a single layer film made of silver (Ag) or a silver alloy and a multilayer film made of the single layer film and a transparent conductive film, which is characterized by remarkably improving the residue (for example, silver residue and/or transparent conductive film residue) and the problem of silver re-adsorption.
Another object of the present invention is to provide a silver thin film etching solution composition that can simultaneously etch the single layer film and the multilayer film.
Another object of the present invention is to provide a thin film etching solution composition which prevents overetching of the single layer film and the multilayer film by an etch stop (etch stop) phenomenon, and which can form a wiring having a small side etch (side etch) and thus can easily form a fine pattern.
Further, an object of the present invention is to provide a silver thin film etching solution composition that maintains etching performance even if the number of processed sheets is increased.
Another object of the present invention is to provide an etching method using the silver thin film etching solution composition.
Another object of the present invention is to provide 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 provides a silver thin film etchant composition comprising: (A) nitric acid; (B-1) an alkylsulfonic acid; (B-2) an organic acid other than an alkylsulfonic acid; (C) one or more of a metal, a metal salt and sulfuric acid; (D) a sulfate salt; and (E) water.
The present invention also provides an etching method using the silver thin film etchant composition.
The present invention also provides a method for forming a metal pattern using the silver thin film etchant composition.
Effects of the invention
The silver thin film etching solution composition of the present invention is used for etching a single layer film made of silver (Ag) or a silver alloy and a multilayer film made of the single layer film and a transparent conductive film, thereby providing an effect of remarkably improving the residue (for example, silver residue and/or transparent conductive film residue) and the problem of silver re-adsorption.
In addition, the silver thin film etchant composition of the present invention provides an effect of improving etching efficiency by simultaneously etching the single layer film and the multi-layer film.
In addition, the silver thin film etching solution composition of the present invention induces an etching stop phenomenon, thereby providing an effect of being able to control an etching rate and adjust a side etch.
In addition, the silver thin film etchant composition of the present invention maintains etching performance even though the number of processed sheets is increased, thereby providing an effect of increasing the lifetime of the etchant composition.
Detailed Description
The invention relates to a silver thin film etching solution composition, an etching method using the same and a method for forming a metal pattern, wherein the silver thin film etching solution composition comprises (A) nitric acid; (B-1) an alkylsulfonic acid; (B-2) an organic acid other than an alkylsulfonic acid; (C) one or more of a metal, a metal salt and sulfuric acid; (D) a sulfate salt; and (E) water.
The silver thin film etchant composition of the present invention, the etching method using the same, and the method for forming a metal pattern are characterized by being used for etching a single layer film made of silver (Ag) or a silver alloy and a multilayer film made of the single layer film and a transparent conductive film, and particularly remarkably improving the problems of residue (for example, silver residue and/or transparent conductive film residue) and silver re-adsorption. The re-adsorption may refer to a phenomenon that silver particles after etching are re-attached to a metal film of an S/D (source/drain) portion exposed in a substrate, and particularly may be re-adsorption of silver to Ti on an upper portion of a Ti/Al/Ti triple-layer film.
The silver thin film etchant composition, the etching method using the same, and the method for forming a metal pattern according to the present invention can be used for simultaneously etching the single layer film and the multilayer film.
The silver thin film etchant composition, the etching method using the same, and the method for forming a metal pattern according to the present invention induce an etch stop phenomenon, thereby providing an effect of controlling an etching rate and adjusting undercut.
The silver thin film etchant composition, the etching method using the same, and the method for forming a metal pattern according to the present invention can provide an effect of increasing the lifetime of the etchant composition by maintaining the etching performance even when the number of processed sheets is increased.
The silver alloy may be in the form of an alloy containing silver as a main component and other metals such as Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W, Pa, and Ti; and silver nitrides, silicides, carbides, oxides, and the like, but are not limited thereto.
The transparent conductive film may include one or more selected from the group consisting of Indium Oxide (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 multilayer film formed in a manner of transparent conductive film/silver, transparent conductive film/silver alloy, transparent conductive film/silver/transparent conductive film, or transparent conductive film/silver alloy/transparent conductive film.
The silver thin film etchant composition, the etching method using the same, and the method for forming a metal pattern according to the present invention can be used for formation of an OLED TFT array substrate for a reflective film, a lead (trace) wire or a nanowire (nanowire) wire for a touch screen panel, but are not limited thereto, and can be used for an electronic component material including the single layer film and the multilayer film.
< silver thin film etching solution composition >
The silver thin film etching solution composition of the present invention comprises (A) nitric acid; (B-1) an alkylsulfonic acid; (B-2) an organic acid other than an alkylsulfonic acid; (C) a metal, one or more of a metal salt and sulfuric acid, and (D) a sulfate, and may contain (E) water as a solvent.
(A) Nitric acid
The nitric acid contained in the silver thin film etching solution composition of the present invention can be used as an oxidizing agent for oxidizing the silver thin film and the transparent conductive film.
The content of the nitric acid may be 7 to 15% by weight, preferably 8 to 12% by weight, based on the total weight of the composition. When the content of the nitric acid is within the above content range, the etching rate can be easily controlled, and the silver thin film and the transparent conductive film can be uniformly etched.
(B) Organic acids
The organic acid contained in the silver thin film etching solution composition of the present invention can be used as an etchant for the silver thin film in etching the silver thin film oxidized by the nitric acid.
The organic acid may contain an organic acid other than (B-1) alkylsulfonic acid and (B-2) alkylsulfonic acid.
(B-1) Alkylsulfonic acid
The alkyl sulfonic acid of the present invention 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, and preferably may be 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 content of the alkylsulfonic acid having 1 to 3 carbon atoms is within the above range, the etching rate of the silver thin film can be easily controlled, and the occurrence of defects due to silver residues and silver re-adsorption can be prevented.
(B-2) organic acids other than alkylsulfonic acids
The organic acid other than the alkylsulfonic acid may include at least one selected from the group consisting of, for example, acetic acid, citric acid, glycolic acid, malonic acid, lactic acid, tartaric acid, butyric acid, formic acid, gluconic acid, oxalic acid, valeric acid, sulfobenzoic acid, sulfosuccinic acid, sulfophthalic acid, salicylic acid, sulfosalicylic acid, benzoic acid, glyceric acid, succinic acid, malic acid, isocitric acid, acrylic acid, iminodiacetic acid, and ethylenediaminetetraacetic acid. As a specific example, the organic acid other than the alkylsulfonic acid may include one or more selected from the group consisting of acetic acid, citric acid, glycolic acid, malonic acid, lactic acid, and tartaric acid, and may preferably include one or more selected from acetic acid and citric acid.
The content of the organic acid other than the alkylsulfonic acid is 25 to 50% by weight, preferably 30 to 45% by weight, based on the total weight of the composition. When the content of the organic acid other than the alkylsulfonic acid is within the above content range, the etching rate of the silver thin film can be easily controlled, and the occurrence of defects due to silver residue and silver re-adsorption can be prevented.
(C) One or more of metal, metal salt and sulfuric acid
One or more of the metal, metal salt and sulfuric acid contained in the silver thin film etchant composition of the present invention may function as an auxiliary etchant for the silver thin film, and may function as a silver residue and a silver re-adsorption inhibitor. Specifically, one or more of the metal, metal salt and sulfuric acid may be used for etching the silver thin film oxidized by the nitric acid and the organic acid and preventing the occurrence of defects due to silver residue and silver re-adsorption after etching.
One or more of the metals, metal salts and sulfuric acid may contain a metal selected from the group consisting of Fe, Cu and the like; fe. Metal salts such as Cu, In and Al; and sulfuric acid, preferably containing the above metal salt. One or more of the metal, the metal salt, and the sulfuric acid may be one or more selected from the group consisting of iron nitrate (ferric nitrate), copper sulfate, indium, and sulfuric acid.
However, when the silver thin film etching solution composition of the present invention contains a chlorine compound (i.e., chloride ions), silver precipitates can be generated by binding with silver (Ag) ions generated during the etching of the silver thin film, and therefore, it is preferable that the silver thin film etching solution composition of the present invention does not contain a chlorine compound.
The content of one or more of the metal, metal salt and sulfuric acid is 0.01 to 3 wt% based on the total weight of the composition, and specifically, 0.01 to 1 wt% is preferable when one or more of the metal and metal salt is contained, and 0.5 to 3 wt% is preferable when the sulfuric acid is contained. When the content of one or more of the metal, the metal salt and the sulfuric acid is within the above content range, it is possible to prevent the occurrence of defects due to silver residue and silver re-adsorption.
(D) Sulfates of sulfuric acid
The sulfate contained in the silver thin film etching solution composition of the present invention is used as an etchant for the transparent conductive film in etching the transparent conductive film.
In addition, the sulfate contained in the silver thin film etching solution composition of the present invention induces the etching stop phenomenon of the silver thin film, thereby preventing the increase of the side etching even if the etching time (etching time) is increased in the etching process.
In other words, the silver thin film etchant composition of the present invention can control the etching rate and adjust the undercut by controlling the occurrence of the etch stop phenomenon by including the sulfate.
The content of the sulfate is preferably 5 to 25 wt%, more preferably 7 to 20 wt%, based on the total weight of the composition. When the content of the sulfate is within the above content range, the etching rate, that is, the etching time in the etching step, can be easily controlled, and the etching stop phenomenon is regularly exhibited, so that the silver thin film and the transparent conductive film can be uniformly etched.
The above-mentioned sulfate may contain one or more selected from the group consisting of potassium bisulfate, sodium bisulfate, ammonium bisulfate, and magnesium sulfate.
(E) Water (W)
The water contained in the silver thin film etching solution composition of the present invention may be deionized water for a semiconductor process, and preferably the deionized water is 18M Ω/cm or more.
In the present invention, the content of water may be the balance, and the balance means the balance to make the total weight of the composition of the present invention containing the essential components and other components than the essential components 100% by weight.
Specifically, the content of the present invention may be 30 to 60% by weight with respect to the total weight of the composition.
The etching solution composition of the present invention preferably does not contain phosphoric acid.
< etching method Using silver thin film etching solution composition >
The present invention also provides an etching method using the silver thin film etchant composition of the present invention. The etching method of the present invention can form a pattern according to a known metal etching method, except for using the silver thin film etchant composition of the present invention.
As an example, the etching method includes: i) forming a single-layer film made of silver or a silver alloy or a multilayer film made of the single-layer film and a transparent conductive film on a substrate; ii) a step of selectively leaving a photoreactive material on the single layer film or the multilayer film; and iii) a step of etching the single-layer film or the multilayer film using the silver thin film etching solution composition of the present invention.
< method for Forming Metal Pattern Using silver thin film etching solution composition >
The present invention also provides a method for forming a metal pattern using the silver thin film etchant composition of the present invention. The method for forming a metal pattern according to the present invention can form a pattern according to a known method for forming a metal pattern, except for using the silver thin film etchant composition of the present invention.
As an example, the method of forming the metal pattern includes: i) forming a single-layer film made of silver or a silver alloy or a multilayer film made of the single-layer film and a transparent conductive film on a substrate; ii) a step of etching the single-layer film or the multilayer film using the silver thin film etching solution composition of the present invention.
The present invention will be described in more detail below with reference to examples. However, the following examples are intended to explain the present invention more specifically, and the scope of the present invention is not limited to the following examples. The scope of the present invention is shown in the claims, and includes all modifications within the meaning and range equivalent to the description of the claims. In the following examples and comparative examples, "%" and "part(s)" indicating the content are based on mass unless otherwise mentioned.
Production of silver thin film etchant compositions of examples and comparative examples
The silver thin film etching solution compositions of examples and comparative examples were manufactured with reference to the following tables 1 and 2.
[ Table 1]
(unit: wt%)
FN: ferric nitrate
[ Table 2]
(unit: wt%)
The following experimental examples were evaluated for the silver thin film etchant compositions of the examples and comparative examples, respectively, assuming that silver (Ag) was not contained in each composition and that Ag concentration reached 1,000ppm in the silver thin film etchant composition after the etching step was performed.
Test example 1: determination of lateral erosion
After an indium oxide/silver/indium oxide three-layer film is formed on a substrate, a photoresist is patterned on the three-layer film. The substrates were subjected to an etching step using the silver thin film etchant compositions of examples and comparative examples.
Over-etching (O/E) was performed at 50% and 100% of the entire region of the three-layer film, based on the time when etching of the region where the photoresist was not patterned was completed. The distance from the end of the photoresist to the silver thin film in the three-layer film was measured by a scanning electron microscope (SEM; model name: SU-8010, Hitachi), and is shown in tables 3 and 4 below.
Test example 2: silver (Ag) residue measurement
After an indium oxide/silver/indium oxide 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 and comparative examples were put into a spray etching type experimental facility (model name: ETCHER (TFT), SEMES Co., Ltd.), and the temperature was raised to 40 ℃ to perform the etching process of the substrate for 120 seconds when the temperature reached 40. + -. 0.1 ℃.
After the etching step is completed, the photoresist is cleaned with deionized water, dried by a hot air drying device, and then removed by a photoresist stripper (PR stripper). After the cleaning and drying, silver residues, which were the phenomenon of silver remaining without being etched in the region where the photoresist was not patterned in the entire area of the three-layer film, were measured for the Array (Array) part and the panel (Pad) part using a scanning electron microscope (SEM; model name: SU-8010, manufactured by hitachi corporation), and evaluated according to the following criteria, and are shown in tables 3 and 4 below.
The following can be understood: the array portion means a region where metal wiring is formed after applying a photoresist and performing an etching process, and the panel portion means a region where no photoresist is applied and an electric signal is transmitted to the metal wiring.
< evaluation criteria for measuring residue >
Very good: is very good
O: good effect
X: failure of the product
Test example 3: silver (Ag) reabsorption assay
After an indium oxide/silver/indium oxide 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 and comparative examples were put into a spray etching type experimental facility (model name: ETCHER (TFT), SEMES Co., Ltd.), and the temperature was raised to 40 ℃ to perform the etching process of the substrate for 120 seconds when the temperature reached 40. + -. 0.1 ℃.
After the etching step is completed, the photoresist is cleaned with deionized water, dried by a hot air drying device, and then removed by a photoresist stripper (PR stripper). After cleaning and drying, the substrate was cut, and its cross section was measured by a scanning electron microscope (SEM; model name: SU-8010, manufactured by Hitachi Co., Ltd.). The number of silver particles adsorbed to the upper Ti of the Ti/Al/Ti triple-layer film exposed in the substrate in the etching step was measured and evaluated according to the following criteria, and shown in tables 3 and 4 below.
< evaluation criteria for silver Re-adsorption >
Very good: is very good
O: good effect
X: failure of the product
Test example 4: evaluation of etching characteristics
After an indium oxide/silver/indium oxide 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 and comparative examples were put into a spray etching type experimental facility (model name: ETCHER (TFT), SEMES Co., Ltd.), and the temperature was raised to 40 ℃ to perform the etching process of the substrate for 120 seconds when the temperature reached 40. + -. 0.1 ℃.
After the etching step is completed, the photoresist is cleaned with deionized water, dried by a hot air drying device, and then removed by a photoresist stripper (PR stripper). After cleaning and drying, the straightness of the metal wiring, the corrosion of the upper film and the lower film, and the like were evaluated according to the following criteria, and are shown in tables 3 and 4 below.
< evaluation criteria >
O: is very good
And (delta): good effect
X: failure of the product
[ Table 3]
[ Table 4]
In tables 3 and 4, the case where the Ag concentration is 0ppm corresponds to the state where the silver thin film etching solution composition was just produced, and the case where the Ag concentration is 1,000ppm corresponds to the state where Ag is dissolved in the silver thin film etching solution composition by performing the etching step.
When the etching process was performed using the silver thin film etchant composition of the example, it was found that the undercut measured over the entire 50 to 100% range was about 0.2 to 0.5 μm when the over-etching was performed, and the undercut at the level desired in the present invention was maintained, and the problems of silver residue and silver re-adsorption did not occur. Further, it was found that even when the number of sheets treated was increased and the silver concentration in the composition was increased (Ag 1,000ppm), the etching properties were excellent without causing the problems of silver residue and re-adsorption, while maintaining the undercut, as compared with the case of the composition immediately before (Ag 0 ppm).
On the other hand, it was confirmed that the problem of silver residue occurred when the etching process was performed using the silver thin film etchant composition of comparative example.
Meanwhile, it is found that when the etching process is performed using the silver thin film etchant composition of the present invention, the lateral etching can be easily adjusted, the problems of silver residue and silver re-adsorption do not occur, and excellent etching performance is provided even if the number of processed sheets is increased.
Claims (9)
1. A silver thin film etching solution composition is characterized by comprising the following components in percentage by weight relative to the total weight of the composition:
(A) 7-15 wt% of nitric acid;
(B-1) 3 to 8 wt% of an alkylsulfonic acid;
(B-2) 25 to 50 wt% of an organic acid other than alkylsulfonic acid;
(C) 0.01-3 wt% of one or more of metal, metal salt and sulfuric acid;
(D) 5-25 wt% of sulfate; and
(E) the balance of water is added into the mixture,
the (D) sulfate salt includes one or more selected from the group consisting of potassium hydrogen sulfate, sodium hydrogen sulfate, ammonium hydrogen sulfate and magnesium sulfate.
2. The silver thin film etching solution composition according to claim 1, wherein the (B-1) alkylsulfonic acid is methanesulfonic acid.
3. The silver thin film etching solution composition according to claim 1, wherein the organic acid other than the (B-2) alkylsulfonic acid comprises at least one selected from the group consisting of acetic acid, citric acid, malonic acid, butyric acid, formic acid, gluconic acid, glycolic acid, oxalic acid, valeric acid, sulfobenzoic 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.
4. The silver thin film etching solution composition according to claim 1, wherein one or more of the (C) metal, metal salt and sulfuric acid comprises a metal selected from the group consisting of Fe and Cu; fe. Metal salts of Cu, In and Al; and sulfuric acid.
5. The silver thin film etching solution composition according to claim 1, wherein the silver thin film etching solution composition is capable of simultaneously etching a single-layer film composed of silver or a silver alloy, or a multilayer film composed of the single-layer film and a transparent conductive film.
6. The silver thin film etching solution composition according to claim 5, wherein the transparent conductive film is one or more 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).
7. The silver thin film etching solution composition according to claim 5, wherein the multilayer film comprises a multilayer film formed of 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.
8. An etching method, comprising:
forming a single-layer film made of silver or a silver alloy or a multilayer film made of the single-layer film and a transparent conductive film on a substrate;
a step of selectively leaving a photoreactive material on the single-layer film or the multilayer film; and
a step of etching the single-layer film or the multilayer film using the silver thin film etching solution composition according to any one of claims 1 to 7.
9. A method of forming a metal pattern, comprising:
forming a single-layer film made of silver or a silver alloy or a multilayer film made of the single-layer film and a transparent conductive film on a substrate; and
a step of etching the single-layer film or the multilayer film using the silver thin film etching solution composition according to any one of claims 1 to 7.
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| KR10-2018-0138517 | 2018-11-12 | ||
| KR1020190110278A KR20200054859A (en) | 2018-11-12 | 2019-09-05 | Etchant composition for silver thin layer and etching method and method for fabrication metal pattern using the same |
| KR20190110290 | 2019-09-05 | ||
| KR10-2019-0110278 | 2019-09-05 | ||
| KR10-2019-0110290 | 2019-09-05 | ||
| KR1020190138687A KR102198608B1 (en) | 2018-11-12 | 2019-11-01 | Etchant composition for silver thin layer and etching method and method for fabrication metal pattern using the same |
| KR10-2019-0138687 | 2019-11-01 |
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| CN1399317A (en) * | 2001-07-23 | 2003-02-26 | 索尼公司 | Etching process and etching liquid |
| KR20090081546A (en) * | 2008-01-24 | 2009-07-29 | 동우 화인켐 주식회사 | Etchant composition for Ag thin layer and method for fabricating metal pattern using the same |
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| KR20170114031A (en) * | 2016-03-31 | 2017-10-13 | 삼성디스플레이 주식회사 | Echant composition and manufacturing method for metal wire |
| CN110158088A (en) * | 2018-02-13 | 2019-08-23 | 东友精细化工有限公司 | Silverskin etchant, engraving method and metal pattern forming method with it |
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| CN1399317A (en) * | 2001-07-23 | 2003-02-26 | 索尼公司 | Etching process and etching liquid |
| KR20090081546A (en) * | 2008-01-24 | 2009-07-29 | 동우 화인켐 주식회사 | Etchant composition for Ag thin layer and method for fabricating metal pattern using the same |
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