CN108342734B - Etching liquid composition, method for producing array substrate for display device, and array substrate - Google Patents
Etching liquid composition, method for producing array substrate for display device, and array substrate Download PDFInfo
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- CN108342734B CN108342734B CN201711227573.8A CN201711227573A CN108342734B CN 108342734 B CN108342734 B CN 108342734B CN 201711227573 A CN201711227573 A CN 201711227573A CN 108342734 B CN108342734 B CN 108342734B
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- 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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- 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
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- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
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- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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- H10D86/01—Manufacture or treatment
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- H10D86/40—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates characterised by multiple TFTs
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- H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10D86/00—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates
- H10D86/40—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates characterised by multiple TFTs
- H10D86/60—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates characterised by multiple TFTs wherein the TFTs are in active matrices
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Abstract
本发明提供蚀刻液组合物、显示装置用阵列基板的制法及阵列基板。该蚀刻液组合物包含过氧化氢5～25重量％；唑化合物0.1～5重量％；乙酸盐和/或乙酸酯化合物0.05～3重量％；硫酸盐化合物0.1～5重量％；和使蚀刻液组合物总重量成为100重量％的余量的水。本发明的蚀刻液组合物具有处理张数优异的效果。此外，本发明的蚀刻液组合物由于不包含含氟化合物，因此不会对玻璃产生损伤，并且具有可以蚀刻金属膜、优选可以蚀刻钼膜的效果。The present invention provides an etchant composition, a method for producing an array substrate for a display device, and an array substrate. The etching solution composition contains 5-25 wt % of hydrogen peroxide; 0.1-5 wt % of an azole compound; 0.05-3 wt % of an acetate and/or acetate compound; 0.1-5 wt % of a sulfate compound; The total weight of the etching liquid composition is the remainder of 100% by weight of water. The etching liquid composition of this invention has the effect which is excellent in the number of sheets processed. Moreover, since the etching liquid composition of this invention does not contain a fluorine-containing compound, it does not damage a glass, and has the effect of being able to etch a metal film, preferably a molybdenum film.
Description
Technical Field
The invention relates to an etching solution composition, a manufacturing method of an array substrate for a display device and the array substrate.
Background
As the information age has been formally entered, the field of displays for processing and displaying a large amount of information has been rapidly developed, and accordingly, 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 (LCD), Plasma Display devices (PDP), Field Emission Display devices (FED), Organic light emitting elements (OLED), and the like, and particularly, Liquid crystal Display devices are drawing attention because of the following characteristics: provides a clear image with excellent resolution, consumes less power, and can produce a display screen in a thin thickness.
A single-layer film of a molybdenum alloy film and an indium oxide film, a multilayer film of a molybdenum alloy film and an indium oxide film, or the like is used for a pixel electrode of a liquid crystal display device such as a TFT-LCD. The pixel electrode is generally completed through a series of photolithography (lithography) processes as follows: a metal film is laminated on a substrate by a method such as sputtering, a photoresist is uniformly applied thereon, light is irradiated through a mask having a pattern formed thereon, a photoresist having a desired pattern is formed by development, the metal film under the photoresist is transferred with a pattern by dry or wet etching, and then the unnecessary photoresist is removed by a stripping step.
When the molybdenum alloy film and the indium oxide film are etched using the same etching solution, although the manufacturing process can be simplified, the molybdenum alloy film generally has a problem that it is difficult to perform wet etching because it has excellent chemical resistance, and the molybdenum alloy film cannot be etched using the oxalic acid-based etching solution for etching the indium oxide film.
As a prior art, Korean laid-open patent No. 10-2014-0025817 discloses an etching solution composition for a molybdenum alloy film, an indium oxide film, or a multilayer film of a molybdenum alloy film and an indium oxide film, which contains 5 to 25 wt% of hydrogen peroxide; 0.1 to 2 wt% of a fluorine compound; 0.001 to 2 wt% of a compound having a sulfonic acid group; 0.1-2 wt% of an anticorrosive agent; 0.01-1 wt% of an auxiliary oxidant; 0.1-5 wt% of hydrogen peroxide stabilizer and water for making the total weight of the whole composition be 100 wt%. However, the above composition has a disadvantage that the etching rate of the molybdenum alloy film and the indium oxide film is insufficient, and the formation of the partial over-etching (over etch) and the Mo — Ti tip (tip) cannot be suppressed. In addition, there is a problem that the lower copper film is etched, and there is a disadvantage that glass (glass) is etched to generate etching stains.
Documents of the prior art
Patent document
Patent document 1: korean laid-open patent No. 10-2014-0025817
Disclosure of Invention
Problems to be solved
The invention aims to provide an etching solution composition which has excellent processing number and does not etch copper films and glass.
In addition, the present invention is directed to a method of manufacturing an array substrate for a display device using the etchant composition and an array substrate for a display device manufactured by the manufacturing method.
Means for solving the problems
In order to achieve the above object, the present invention provides an etching solution composition comprising, relative to the total weight of the composition:
5-25 wt% of hydrogen peroxide;
0.1 to 5 wt% of an azole compound;
0.05 to 3 wt% of an acetate and/or acetate compound;
0.1 to 5 wt% of a sulfate compound; and
water in the balance of 100 wt% based on the total weight of the etching solution composition.
Further, the present invention provides a method of manufacturing an array substrate for a display device, comprising:
(a) a step of forming a gate wiring on a substrate;
(b) forming a gate insulating layer on the substrate including the gate wiring;
(c) forming a semiconductor layer on the gate insulating layer;
(d) forming a source electrode and a drain electrode on the semiconductor layer; and
(e) a step of forming a pixel electrode connected to the drain electrode,
the step (e) includes a step of forming a pixel electrode by etching using the etchant composition of the present invention.
The present invention also provides an array substrate for a display device manufactured by the manufacturing method of the present invention.
Effects of the invention
The etching solution composition of the present invention has an excellent effect of processing the number of sheets.
Further, the etching liquid composition of the present invention does not contain a fluorine-containing compound, and therefore has an effect of being able to etch a metal film, preferably a molybdenum film, without damaging glass.
Detailed Description
The present invention will be described in more detail below.
The invention relates to an etching solution composition, which comprises the following components in percentage by weight relative to the total weight of the composition:
5-25 wt% of hydrogen peroxide;
0.1 to 5 wt% of an azole compound;
0.05 to 3 wt% of an acetate and/or acetate compound;
0.1 to 5 wt% of a sulfate compound; and
water in the balance of 100 wt% based on the total weight of the etching solution composition.
The etchant composition of the present invention can etch a molybdenum-containing metal film, and preferably, a single-layer film made of molybdenum or a molybdenum alloy, or a multilayer film including the single-layer film can be used.
The molybdenum alloy film may be a nitride of molybdenum, an oxide of molybdenum, and a molybdenum alloy film including one or more metals selected from the group consisting of neodymium (Nd), tantalum (Ta), indium (In), copper (Cu), palladium (Pd), niobium (Nb), nickel (Ni), chromium (Cr), magnesium (Mg), tungsten (W), protactinium (Pa), and titanium (Ti).
The multilayer film may be a multilayer film including a molybdenum-containing metal film and a transparent conductive film, but is not limited thereto.
Specific examples of the transparent conductive film include Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), Indium Tin Zinc Oxide (ITZO), Indium Gallium Zinc Oxide (IGZO), and the like, but the transparent conductive film is not limited thereto.
The components constituting the etching liquid composition of the present invention will be described below.
(A) Hydrogen peroxide (H)2O2)
The hydrogen peroxide contained in the etching liquid composition of the present invention functions as a main dissociation agent that affects the etching of the molybdenum-containing metal film.
The content of the hydrogen peroxide is 5 to 25 wt%, preferably 7 to 15 wt%, based on the total weight of the etching solution composition of the present invention.
If the content of hydrogen peroxide is less than 5% by weight, the etching capability of the molybdenum-containing metal film is insufficient and sufficient etching cannot be achieved, and if the content exceeds 25% by weight, the etching rate is increased and the process control is difficult.
(B) Azole compounds
The azole compound contained in the etching liquid composition of the present invention plays a role in reducing the etching rate of the molybdenum-containing metal film and in preventing corrosion of the copper metal film.
The kind of the azole compound is not particularly limited as long as it is an azole compound used in the art, but an azole compound having 1 to 30 carbon atoms is preferably used. More preferably, at least one selected from the group consisting of triazole-based compounds, aminotetrazole-based compounds, imidazole-based compounds, indole-based compounds, purine-based compounds, pyrazole-based compounds, pyridine-based compounds, pyrimidine-based compounds, pyrrole-based compounds, pyrrolidine-based compounds, and pyrroline-based compounds can be used, but the present invention is not limited thereto.
The azole compound is contained in an amount of 0.1 to 5 wt%, preferably 0.2 to 1 wt%, based on the total weight of the etching solution composition of the present invention.
If the content of the above azole compound is less than 0.1 wt%, the copper metal film may be etched, and if the content exceeds 5 wt%, the etching rate of the molybdenum-containing metal film becomes slow and a loss of process time may occur.
(C) Acetate and/or acetate compounds
The acetate and/or acetate compound contained in the etching solution composition of the present invention functions as a main decomposer that affects the etching of the molybdenum-containing metal film. Conventionally, a fluorine-containing compound has been used as a main debonder for etching a molybdenum-containing metal film, but when a fluorine-containing compound is used, there is a problem that a glass substrate is etched and etching unevenness occurs. Therefore, in the present invention, in order to solve the above-mentioned problems, it is desired to use an acetate and/or an acetate compound which can function as a fluorine-containing compound and can prevent etching of a glass substrate, instead of the fluorine-containing compound.
The acetate and/or acetate compound includes one or more selected from the group consisting of ethyl acetate, sodium acetate, methyl acetate, potassium acetate, and ammonium acetate.
The content of the acetate and/or acetate compound is 0.05 to 3 wt%, preferably 0.1 to 1 wt%, based on the total weight of the etching solution composition of the present invention.
If the content of the acetate and/or acetate compound is less than 0.05 wt%, an etching residue is generated, and if the content exceeds 3 wt%, the etching rate of the molybdenum-containing metal film is too high, which makes it difficult to control the process.
(D) Sulfate compounds
The sulfate compound contained in the etching liquid composition of the present invention functions to increase the number of etching processed sheets. Therefore, if the sulfate compound is not used as the etching liquid composition, there is a disadvantage that the number of processed sheets is low.
The sulfate compound includes one or more selected from the group consisting of sodium sulfate, potassium sulfate, and ammonium sulfate.
The content of the sulfate compound is 0.1 to 5 wt%, preferably 0.1 to 1 wt%, based on the total weight of the etching solution composition of the present invention.
If the content of the sulfate compound is less than 0.1 wt%, there is a disadvantage that the number of processed sheets is reduced, and if the content exceeds 5 wt%, there is a disadvantage that damage (damage) is generated in the copper film.
(E) Water (W)
The water contained in the etching solution composition of the present invention is not particularly limited, but deionized water is preferably used, and as the deionized water, deionized water having a resistivity value of 18M Ω/. cm or more used in a semiconductor process is preferably used.
The etching solution composition of the present invention may further comprise one or more selected from the group consisting of an etching regulator, a surfactant, a sequestering agent, a pH regulator, and other additives not limited thereto, in addition to the above-mentioned components. In order to achieve the effects of the present invention within the scope of the present invention, the above additives may be selected from those commonly used in the art.
The components constituting the etchant composition of the present invention preferably have a purity for use in a semiconductor process.
Further, the present invention relates to a method for manufacturing an array substrate for a display device, including:
(a) a step of forming a gate wiring on a substrate;
(b) forming a gate insulating layer on the substrate including the gate wiring;
(c) forming a semiconductor layer on the gate insulating layer;
(d) forming a source electrode and a drain electrode on the semiconductor layer; and
(e) a step of forming a pixel electrode connected to the drain electrode,
the step (e) includes a step of forming a pixel electrode by etching using the etchant composition of the present invention.
The pixel electrode is preferably a molybdenum-containing metal film, and the pixel electrode can be manufactured by etching the metal film using the etchant composition of the present invention.
The same applies to the contents of the molybdenum-containing metal film.
The array substrate for a display device may be a Thin Film Transistor (TFT) array substrate.
The present invention also relates to an array substrate for a display device manufactured by the manufacturing method of the present invention.
The present invention will be described in more detail below with reference to examples and comparative examples. However, the following examples are only for illustrating the present invention, and the present invention is not limited to the following examples, and various modifications and changes can be made. The scope of the invention is defined by the technical idea of the scope of the appended claims.
Examples 1 to 23 and comparative examples 1 to 11 preparation of etching liquid composition
The etchant compositions of examples 1 to 23 and comparative examples 1 to 11 were prepared with the compositions and contents shown in table 1 below, and the balance of deionized water was added so that the total weight of the composition became 100 wt%.
[ Table 1] (wt%)
PA: potassium acetate
AA: ammonium acetate
And SS: sodium sulfate
AS: ammonium sulfate
Experimental example 1 evaluation of characteristics of etching solution composition
A molybdenum alloy film (Mo-Nb) was vapor-deposited on a glass substrate (100 mm. times.100 mm), a photoresist having a predetermined pattern was formed on the substrate by a photolithography (photolithography) process, and then an etching process was performed using the etchant compositions of examples 1 to 23 and comparative examples 1 to 11, respectively.
In a jet etching system test apparatus (model name: ETCHER (TFT), SEMES), the temperature of the etching solution composition in the etching step is about 30 ℃, but the appropriate temperature may be changed as necessary depending on other process conditions and other factors. The etching time varies depending on the etching temperature, but is usually about 100 seconds. The results of examining whether or not the residue of the molybdenum alloy film and the damage (damage) of the glass substrate etched in the etching step were detected by SEM (product of hitachi corporation, model number S-4700) are shown in table 2 below.
The following table 2 shows the results of performing an etching process to detect whether or not the copper substrate is damaged (damage) in the same manner as in the above-described case where the glass substrate is vapor-deposited with a copper film instead of the molybdenum alloy film (Mo — Nb).
Further, 300ppm to 3000ppm of Mo — Nb as a molybdenum alloy was added to the etching solution composition, and the amount of change in side etching (S/E) according to the number of processed sheets was observed, and the results are shown in table 2 below.
[ Table 2]
From the results in table 2, it is clear that examples 1 to 23 as the etchant composition of the present invention did not generate molybdenum alloy film residue, were excellent in the amount of change in undercut depending on the number of processed sheets, and did not cause damage to copper or glass substrates.
On the other hand, the etching solution composition of comparative example 1, in which the hydrogen peroxide content is less than the range of the present invention, could not etch the molybdenum alloy film, and thus the amount of change in undercut depending on the number of processed sheets could not be measured. The etchant composition of comparative example 2 having a hydrogen peroxide content exceeding the range of the present invention exhibited a Pattern missing (Pattern Out) phenomenon, and the amount of undercut change according to the number of processed sheets could not be confirmed.
The etching solution composition of comparative example 3 containing no azole compound damages the copper substrate, and the etching solution composition of comparative example 4 containing an azole compound in an amount exceeding the range of the present invention cannot etch the molybdenum alloy film, and therefore cannot measure the amount of change in undercut depending on the number of processed sheets.
The etching solution composition of comparative example 5 not containing acetate and/or acetate was not able to etch the molybdenum alloy film, and therefore, the amount of change in undercut according to the number of processed sheets was not able to be measured, and the etching solution composition of comparative example 6 having an acetate and/or acetate content exceeding the range of the present invention exhibited a pattern missing phenomenon and was not able to confirm the amount of change in undercut according to the number of processed sheets.
The etching solution composition of comparative example 7 containing no sulfate was not etched at 2000ppm and the number of processed sheets was not good, and the etching solution composition of comparative example 8 containing sulfate exceeding the range of the present invention damaged the copper substrate.
The etching liquid composition of comparative example 9 containing no acetate and/or acetate and sulfate but containing a fluorine-containing compound was not etched at 2000ppm and the number of processed sheets was not good, so that
The speed of/sec causes damage to the glass substrate.
The etching solution composition of comparative example 10 containing no acetate and/or acetate but containing a fluorine-containing compound, and
the speed of/sec causes damage to the glass substrate.
The etchant composition of comparative example 11, which did not contain acetate and/or acetate but contained an organic acid, damaged the copper substrate.
Therefore, it was confirmed that the etchant composition of the present invention has the effects of not causing residue on the molybdenum film when etching the substrate, having an excellent number of processed sheets, and not damaging the copper and glass substrates.
Claims (8)
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| KR1020170010264A KR102700386B1 (en) | 2017-01-23 | 2017-01-23 | Etching solution composition and manufacturing method of an array substrate for display device using the same |
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| KR20140118318A (en) * | 2013-03-28 | 2014-10-08 | 동우 화인켐 주식회사 | Etchant composition for copper-containing metal layer and preparing method of an array substrate for liquid crystal display using same |
| KR102293674B1 (en) * | 2015-03-24 | 2021-08-25 | 동우 화인켐 주식회사 | Etching solution composition for copper-based metal layer and method for etching copper-based metal layer using the same |
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| CN102648269A (en) * | 2009-11-16 | 2012-08-22 | 东友Fine-Chem股份有限公司 | Etchant composition for a single molybdenum film |
| CN105369249A (en) * | 2014-08-25 | 2016-03-02 | 乐金显示有限公司 | Etchant composition and method for manufacturing thin film transistor array substrate |
| CN105655418A (en) * | 2015-12-30 | 2016-06-08 | 芜湖奕辰模具科技有限公司 | Texturing process of thin-film cell |
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| KR20180086622A (en) | 2018-08-01 |
| CN108342734A (en) | 2018-07-31 |
| KR102700386B1 (en) | 2024-08-30 |
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