CN106367755B - Etchant composition, method of manufacturing array substrate for liquid crystal display device using the same, and array substrate - Google Patents

Etchant composition, method of manufacturing array substrate for liquid crystal display device using the same, and array substrate Download PDF

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CN106367755B
CN106367755B CN201610121704.3A CN201610121704A CN106367755B CN 106367755 B CN106367755 B CN 106367755B CN 201610121704 A CN201610121704 A CN 201610121704A CN 106367755 B CN106367755 B CN 106367755B
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acid
copper
cis
balance
weight
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CN106367755A (en
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鞠仁说
南基龙
崔汉永
刘仁浩
金宝衡
李钟文
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Dongwoo Fine Chem Co Ltd
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Priority claimed from KR1020150105204A external-priority patent/KR102423604B1/en
Priority claimed from KR1020150105041A external-priority patent/KR102423605B1/en
Priority claimed from KR1020150105157A external-priority patent/KR102400312B1/en
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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
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • 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
    • 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
    • C23F1/26—Acidic compositions for etching refractory metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
    • H—ELECTRICITY
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Metallurgy (AREA)
  • 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)
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Abstract

The present invention relates to an etchant composition, and a method of manufacturing an array substrate for a liquid crystal display device and an array substrate using the same. When the etchant composition of the present invention is used to etch a copper-based metal layer, an excellent etching profile and a large number of work sheets are obtained.

Description

Etchant composition, method of manufacturing array substrate for liquid crystal display device using the same, and array substrate
Technical Field
The present invention relates to an etchant composition, a method of manufacturing an array substrate for a liquid crystal display device using the same, and an array substrate.
Background
thin Film Transistors (TFTs) are typical electronic circuits for driving semiconductor devices and flat panel displays. The TFT manufacturing process typically includes forming a metal layer as a material of the gate and data lines on a substrate, and forming a photoresist on selected areas of the metal layer, and then etching the metal layer using the photoresist as a mask.
The gate and data lines use copper having good electrical conductivity and low resistance, and in the case of copper, coating and patterning of a photoresist may be difficult in terms of processes, and thus, a copper-based metal layer has recently been used as the gate and data lines instead of a separate copper layer. Among the copper-based metal layers, a titanium/copper double layer is generally used. However, when the titanium/copper double layer is etched at the same time, there are disadvantages that the etching profile is poor and it is difficult to perform post-processing, and copper elution occurs as the etching progresses, which results in a small number of processed plates. In view of the above, an etchant composition for copper-based metal layers has been actively studied, and as an example, korean patent application publication No.2015-0059800 provides a liquid composition comprising a source of maleic acid ions, a source of copper ions, and a source of fluoride ions, and having a pH of 0 to 7. However, the liquid composition has disadvantages in that it has a poor etching profile and the number of processed plates is reduced.
Therefore, there is a continuing need for etchant compositions that have excellent etch profiles and high numbers of processed plates when etching copper-based metal layers, such as titanium/copper bilayers.
[ Prior art documents ]
[ patent document ]
Korean patent application publication No.2015-0059800
Disclosure of Invention
an object of the present invention is to provide an etchant composition for a copper-based metal layer, which has an excellent etching profile and is high in the number of processed boards.
in view of the above, one aspect of the present invention provides an etchant composition for copper-based metals, comprising,
0.5 to 10% by weight of a copper compound;
0.01 to 2% by weight of a fluorine compound;
1 to 10% by weight of one or more types of inorganic acids selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and perchloric acid;
0.1 to 10% by weight of one or more types of chlorine compounds selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride, ammonium chloride, methanesulfonyl chloride, ethanesulfonyl chloride, chlorobenzenesulfonyl chloride, benzenesulfonyl chloride and chloroethanesulfonyl chloride;
1 to 10% by weight of one or more types of organic acids selected from the group consisting of acetic acid, butyric acid, citric 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, malic acid, tartaric acid, isocitric acid, propionic acid (profenoic acid), iminodiacetic acid, and ethylenediaminetetraacetic acid, or a salt thereof;
0.1 to 10% by weight of one or more types of non-metallic inorganic salts selected from the group consisting of ammonium sulfate, sodium sulfate, potassium sulfate, calcium sulfate, ammonium bisulfate, sodium bisulfate, potassium bisulfate, calcium hydrogen sulfate, ammonium nitrate, sodium nitrate, potassium nitrate and calcium nitrate;
0.01 to 5% by weight of a cyclic amine compound;
0.5 to 10% by weight of a chelating agent; and
The balance of water is added into the mixture,
Wherein the chelating agent is
1) A cis-dicarboxylic acid or a salt thereof,
2) One or more types selected from the group consisting of maleic acid, citraconic acid, phthalic acid, 1,2,4, 5-benzenetetracarboxylic acid, mellitic acid, 4-sulfophthalic acid, quinolinic acid, cis-5-norbornene-exo-2, 3-dicarboxylic acid, 1,2,3, 4-cyclobutanetetracarboxylic acid and cis, cis-1, 2,3, 4-cyclopentanetetracarboxylic acid, or a salt thereof, or
3) One or more types selected from the group consisting of malonic acid, succinic acid, and glutaric acid, or salts thereof.
In one embodiment, the chelating agent may be one or more types selected from the group consisting of: maleic anhydride, citraconic anhydride, 2, 3-dimethylmaleic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, phenylmaleic anhydride, 2,3-dihydro-1, 4-dithio [2,3-C ] furan-5,7-dione (2,3-dihydro-1,4-dithino [2,3-C ] furan-5,7-dione), phthalic anhydride, 4-methylphthalic anhydride, pyromellitic dianhydride, 3-oxabicyclo [3,1,0] -hexane-2, 4-dione, cis-1, 2,3, 4-cyclopentanetetracarboxylic dianhydride, cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride, cis-5-norbornene-exo-2, 3-dicarboxylic anhydride, cis-1, 2,3, 6-tetrahydrophthalic anhydride, maleic acid, citraconic acid, phthalic acid, 1,2,4, 5-benzenetetracarboxylic acid, mellitic acid, and 4-sulfophthalic acid; or a salt thereof.
In another embodiment, the copper-based metal layer may be a double layer of titanium or a titanium alloy and copper or a copper alloy.
Another aspect of the present invention provides a method of manufacturing an array substrate for a liquid crystal display device, the method including,
a) Forming a gate line on a substrate;
b) Forming a gate insulating layer on the substrate including the gate line;
c) Forming a semiconductor layer on the gate insulating layer;
d) Forming source and drain electrodes on the semiconductor layer; and
e) Forming a pixel electrode connected to the drain electrode,
Wherein the step a) or d) includes forming a copper-based metal layer on the substrate or the semiconductor layer and etching the copper-based metal layer with the etchant composition to form a gate line, or source and drain electrodes, and
The etchant composition comprising, relative to the total weight of the composition, 0.5 to 10% by weight of a copper compound; 0.01 to 2% by weight of a fluorine compound; 1 to 10% by weight of one or more types of inorganic acids selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and perchloric acid; 0.1 to 10% by weight of one or more types of chlorine compounds selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride, ammonium chloride, methanesulfonyl chloride, ethanesulfonyl chloride, chlorobenzenesulfonyl chloride, benzenesulfonyl chloride and chloroethanesulfonyl chloride; 1 to 10% by weight of one or more types of organic acids selected from the group consisting of acetic acid, butyric acid, citric 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, malic acid, tartaric acid, isocitric acid, propionic acid, iminodiacetic acid, and ethylenediaminetetraacetic acid, or a salt thereof; 0.1 to 10% by weight of one or more types of non-metallic inorganic salts selected from the group consisting of ammonium sulfate, sodium sulfate, potassium sulfate, calcium sulfate, ammonium bisulfate, sodium bisulfate, potassium bisulfate, calcium hydrogen sulfate, ammonium nitrate, sodium nitrate, potassium nitrate and calcium nitrate; 0.01 to 5% by weight of a cyclic amine compound; 0.5 to 10% by weight of a chelating agent; and the balance water.
In one embodiment, the array substrate of the liquid crystal display device may be a Thin Film Transistor (TFT) array substrate.
In another embodiment, the chelating agent may be one or more types selected from the group consisting of: maleic anhydride, citraconic anhydride, 2, 3-dimethylmaleic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, phenylmaleic anhydride, 2,3-dihydro-1, 4-dithio [2,3-C ] furan-5,7-dione, phthalic anhydride, 4-methylphthalic anhydride, pyromellitic dianhydride, 3-oxabicyclo [3,1,0] -hexane-2, 4-dione, cis-1, 2,3, 4-cyclopentanetetracarboxylic dianhydride, cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride, cis-5-norbornene-exo-2, 3-dicarboxylic anhydride, cis-1, 2,3, 6-tetrahydrophthalic anhydride, maleic acid, citraconic acid, phthalic acid, 1,2,4, 5-benzenetetracarboxylic acid, mellitic acid and 4-sulfophthalic acid; or a salt thereof.
In another embodiment, the copper-based metal layer may be a double layer of titanium or a titanium alloy and copper or a copper alloy.
Still another aspect of the present invention provides an array substrate for a liquid crystal display device manufactured using the above method.
Drawings
The objects and nature of the invention will become apparent from the following description of embodiments thereof, given in conjunction with the accompanying drawings, wherein:
FIG. 1 shows a cross section when a titanium/copper bilayer is etched using the etchant compositions of example 1 and comparative example 12;
FIG. 2 shows a cross section when a titanium/copper bilayer is etched using the etchant compositions of example 17 and comparative example 27; and
FIG. 3 shows a cross section when the titanium/copper bilayer was etched using the etchant compositions of example 32 and comparative example 42.
Detailed Description
The present invention relates to an etchant composition, and a method of manufacturing an array substrate for a liquid crystal display device.
The etchant composition of the present invention has an excellent etching profile and a large number of process plates when etching a copper-based metal layer by including a certain content of a specific chelating agent.
Hereinafter, the present invention will be described in detail.
etching composition
in the present invention, the copper compound functions as an oxidizing agent and maintains CD shift when the etchant etches the metal layer, and preferably accounts for 0.5 to 10 wt% relative to the total weight of the etchant. When the content is less than 0.5 wt%, etching of copper or a metal layer containing copper cannot be achieved, or the etching rate is very low and the initial etching is not uniform. When the content is more than 10% by weight, the effect of increasing the number of processed sheets is not obtained. The copper compound is preferably used in one or more types selected from the group consisting of copper sulfate, copper chloride and copper nitrate.
The fluorine compound is a main component for etching titanium or a metal layer containing titanium and plays a role in removing residues that may occur during etching. The fluorine compound preferably accounts for 0.01 to 2 wt% relative to the total weight of the etchant. When the content of the fluorine compound is less than 0.01 wt%, an etching rate of titanium or a metal layer including titanium is reduced, causing a residue, and when the content is more than 2.0 wt%, damage to a substrate such as glass on which a metal line is formed and damage to an insulating layer including silicon formed therewith may occur. The fluorine compound may use a compound in which fluorine ions or polyatomic fluorine ions are dissociated in a solution, and preferably one or more types selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, and potassium bifluoride are used.
One or more types of inorganic acids selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, and perchloric acid are auxiliary oxidizing agents for etching copper or a metal layer containing copper and titanium or a metal layer containing titanium, and preferably account for 1 to 10% by weight relative to the total weight of the etchant. When the content of the inorganic acid is less than 1% by weight, the etching rate of copper or a metal layer containing copper and titanium or a metal layer containing titanium is reduced, which may cause etching profile defects and residues, and when the content is more than 10% by weight, over-etching and photoresist cracking occur, which may cause line short due to liquid chemical permeation.
One or more types of chlorine compounds selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride, ammonium chloride, methanesulfonyl chloride, ethanesulfonyl chloride, chlorobenzenesulfonyl chloride, benzenesulfonyl chloride, and chloroethanesulfonyl chloride act as an auxiliary oxidant for the metal layer, control the etching rate and the angle of the metal layer, and have an advantage of preventing wire exposure. The chlorine compound preferably represents from 0.1% to 10% by weight relative to the total weight of the composition. When the content of the chlorine compound is less than 0.1 wt%, the etching rate for copper is reduced, causing an increase in etching time in the process, which may cause a problem in productivity. In addition, when the content is more than 10% by weight, overetching may occur because the etching rate of copper cannot be controlled.
One or more types of organic acids selected from the group consisting of acetic acid, butyric acid, citric 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, malic acid, tartaric acid, isocitric acid, propionic acid, iminodiacetic acid, and ethylenediaminetetraacetic acid, or a salt thereof, play a role of controlling an etching rate and a chelating agent by increasing the solubility of copper ions occurring during precipitation, and lower pH. The organic acid or salt thereof is preferably present in an amount of 1 to 10% by weight relative to the total weight of the etchant. When the content of the organic acid or the organic acid salt is less than 1% by weight, the effect of increasing the number of processed boards is not obtained, and when the content is more than 10% by weight, over-etching occurs, which may cause a line short circuit.
One or more types of non-metallic inorganic salts selected from the group consisting of ammonium sulfate, sodium sulfate, potassium sulfate, calcium sulfate, ammonium bisulfate, sodium bisulfate, potassium bisulfate, calcium bisulfate, ammonium nitrate, sodium nitrate, potassium nitrate, and calcium nitrate, function as an auxiliary etching control agent for the metal layer, and have the effect of improving an inferior etching profile, which is a disadvantage of an etchant containing a chlorine compound. The non-metallic inorganic salt preferably represents from 0.1% to 10% by weight relative to the total weight of the composition. When the content is less than 0.1% by weight, the effect of assisting the etching control agent and improving the etching profile cannot be achieved, and when the content is more than 10% by weight, over-etching may occur.
The cyclic amine compound is an etching control agent that controls batch etching and the angle of copper or a metal layer containing copper. The cyclic amine compound preferably accounts for 0.01 to 5 wt% relative to the total weight of the composition. When the content is less than 0.01 wt%, uniform etching of the metal layer may not be obtained, and when the content is more than 5 wt%, the etching rate may be reduced. The cyclic amine compound preferably uses one or more types selected from the group consisting of 5-aminotetrazole, triazole, phenyltetrazole, imidazole, indole, purine, pyrazole, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, and 5-methyltetrazole.
water means deionized water, and water for semiconductor processing is used, and it is preferable to use water of 18 M.OMEGA./cm or more. Water makes up the balance relative to the total content of the etchant, so that the total weight of the etchant becomes 100 wt%.
The chelating agent of the present invention plays a role as a main component for increasing the number of processed boards.
In particular, the chelating agent may be
1) A cis-dicarboxylic acid or a salt thereof,
2) one or more types selected from the group consisting of maleic acid, citraconic acid, phthalic acid, 1,2,4, 5-benzenetetracarboxylic acid, mellitic acid, 4-sulfophthalic acid, quinolinic acid, cis-5-norbornene-exo-2, 3-dicarboxylic acid, 1,2,3, 4-cyclobutanetetracarboxylic acid and cis, cis-1, 2,3, 4-cyclopentanetetracarboxylic acid, or a salt thereof, or
3) one or more types selected from the group consisting of malonic acid, succinic acid, and glutaric acid, or salts thereof.
The cis-dicarboxylic acid or a salt thereof may be one or more types selected from the group consisting of: maleic anhydride, citraconic anhydride, 2, 3-dimethylmaleic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, phenylmaleic anhydride, 2,3-dihydro-1, 4-dithio [2,3-C ] furan-5,7-dione, phthalic anhydride, 4-methylphthalic anhydride, pyromellitic dianhydride, 3-oxabicyclo [3,1,0] -hexane-2, 4-dione, cis-1, 2,3, 4-cyclopentanetetracarboxylic dianhydride, cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride, cis-5-norbornene-exo-2, 3-dicarboxylic anhydride, cis-1, 2,3, 6-tetrahydrophthalic anhydride, maleic acid, citraconic acid, phthalic acid, 1,2,4, 5-benzenetetracarboxylic acid, mellitic acid and 4-sulfophthalic acid; or a salt thereof.
The chelating agent preferably represents from 0.5% to 10% by weight relative to the total weight of the composition. When the content is less than 0.5% by weight, the effect of increasing the number of processed plates is not obtained, and when the content is more than 10% by weight, the etching rate of the metal layer increases, which may cause over-etching.
In the present invention, the etchant composition may further include a metal ion chelating agent, a corrosion inhibitor, and the like.
Method of manufacturing array substrate for liquid crystal display device
A method of manufacturing an array substrate for a liquid crystal display device, the method comprising,
a) Forming a gate line on a substrate;
b) Forming a gate insulating layer on the substrate including the gate line;
c) Forming a semiconductor layer on the gate insulating layer;
d) forming source and drain electrodes on the semiconductor layer; and
e) Forming a pixel electrode connected to the drain electrode,
Wherein the step a) or d) includes forming a copper-based metal layer on the substrate or the semiconductor layer, and etching the copper-based metal layer with the etchant composition of the present invention to form a gate line, or source and drain electrodes.
The array substrate of the liquid crystal display device may be a Thin Film Transistor (TFT) array substrate, but is not limited thereto, and may also be used to manufacture other electronic devices including metal lines formed with a copper-based metal layer, for example, to manufacture a memory semiconductor display panel.
Hereinafter, the present invention will be described in more detail with reference to examples, comparative examples and test examples. However, the following examples, comparative examples and test examples are for illustrative purposes only, the scope of the present invention is not limited to the following examples, comparative examples and test examples, and may be variously modified and changed.
Examples 1 to 48 and comparative examples 1 to 46 preparation of etchant compositions
The etchant compositions were prepared with the compositions and contents (unit: weight%) listed in the following tables 1,2 and 3.
[ Table 1]
Categories of (A) (B) (C) (D) (E) (F) (G) (H) (I) (J) (K) Water (W)
Example 1 3 0.5 5 6 2 3 1 2 - - - Balance of
example 2 0.5 0.5 5 6 2 3 1 2 - - - Balance of
Practice ofExample 3 10 0.5 5 6 2 3 1 2 - - - Balance of
Example 4 3 0.5 1 6 2 3 1 2 - - - Balance of
example 5 3 0.5 10 6 2 3 1 2 - - - Balance of
Example 6 3 0.5 5 1 2 3 1 2 - - - balance of
Example 7 3 0.5 5 10 2 3 1 2 - - - Balance of
Example 8 3 0.5 5 6 0.3 3 1 2 - - - Balance of
Example 9 3 0.5 5 6 10 3 1 2 - - - Balance of
Example 10 3 0.5 5 6 2 1 1 2 - - - Balance of
Example 11 3 0.5 5 6 2 10 1 2 - - - Balance of
Example 12 3 0.5 5 6 2 3 0.05 2 - - - Balance of
example 13 3 0.5 5 6 2 3 5 2 - - - balance of
Example 14 3 0.5 5 6 2 3 1 1 - - - Balance of
example 15 3 0.5 5 6 2 3 1 10 - - - Balance of
example 16 3 0.5 5 6 2 3 1 - 2 - - Balance of
Comparative example 1 3 0.5 5 6 2 3 1 - - - - Balance of
Comparative example 2 3 0.5 5 6 2 3 1 - - - 2 Balance of
Comparative example 3 3 0.5 5 6 2 3 1 - - 2 - Balance of
Comparative example 4 - 0.5 5 6 2 3 1 2 - - - balance of
Comparative example 5 13 0.5 5 6 2 3 1 2 - - - Balance of
Comparative example 6 3 0.5 0.5 6 2 3 1 2 - - - balance of
Comparative example 7 3 0.5 13 6 2 3 1 2 - - - balance of
Comparative example 8 3 0.5 5 - 2 3 1 2 - - - Balance of
Comparative example 9 3 0.5 5 13 2 3 1 2 - - - Balance of
Comparative example 10 3 0.5 5 6 0 3 1 2 - - - Balance of
Comparative example 11 3 0.5 5 6 13 3 1 2 - - - Balance of
Comparative example 12 3 0.5 5 6 2 0 1 2 - - - Balance of
Comparative example 13 3 0.5 5 6 2 13 1 2 - - - Balance of
Comparative example 14 3 0.5 5 6 2 3 0 2 - - - Balance of
comparative example 15 3 0.5 5 6 2 3 7 2 - - - Balance of
Comparative example 16 3 0.5 5 6 2 3 1 13 - - - Balance of
[ Table 2]
Categories of (A) (B) (C) (D) (E) (F) (G) (L) (M) Water (W)
Example 17 3 0.5 5 6 2 3 1 2 - balance of
Example 18 0.5 0.5 5 6 2 3 1 2 - Balance of
Example 19 10 0.5 5 6 2 3 1 2 - Balance of
Example 20 3 0.5 1 6 2 3 1 2 - balance of
Example 21 3 0.5 10 6 2 3 1 2 - Balance of
Example 22 3 0.5 5 1 2 3 1 2 - Balance of
Example 23 3 0.5 5 10 2 3 1 2 - Balance of
Example 24 3 0.5 5 6 0.3 3 1 2 - Balance of
Example 25 3 0.5 5 6 10 3 1 2 - Balance of
Example 26 3 0.5 5 6 2 1 1 2 - Balance of
Example 27 3 0.5 5 6 2 10 1 2 - Balance of
Example 28 3 0.5 5 6 2 3 0.05 2 - Balance of
Example 29 3 0.5 5 6 2 3 5 2 - Balance of
Example 30 3 0.5 5 6 2 3 1 1 - Balance of
example 31 3 0.5 5 6 2 3 1 10 - Balance of
Comparative example 17 3 0.5 5 6 2 3 1 - - Balance of
Comparative example 18 3 0.5 5 6 2 3 1 - 2 Balance of
Comparative example 19 - 0.5 5 6 2 3 1 2 - Balance of
Comparative example 20 13 0.5 5 6 2 3 1 2 - Balance of
Comparative example 21 3 0.5 0.5 6 2 3 1 2 - Balance of
Comparative example 22 3 0.5 13 6 2 3 1 2 - balance of
Comparative example 23 3 0.5 5 - 2 3 1 2 - Balance of
comparative example 24 3 0.5 5 13 2 3 1 2 - balance of
comparative example 25 3 0.5 5 6 0 3 1 2 - Balance of
comparative example 26 3 0.5 5 6 13 3 1 2 - Balance of
Comparative example 27 3 0.5 5 6 2 0 1 2 - Balance of
Comparative example 28 3 0.5 5 6 2 13 1 2 - balance of
Comparative example 29 3 0.5 5 6 2 3 0 2 - Balance of
Comparative example 30 3 0.5 5 6 2 3 7 2 - Balance of
Comparative example 31 3 0.5 5 6 2 3 1 13 - Balance of
[ Table 3]
categories of (A) (B) (C) (D) (E) (F) (G) (N) (O) (P) (Q) Water (W)
Example 32 3 0.5 5 6 2 3 1 2 - - - balance of
Example 33 0.5 0.5 5 6 2 3 1 2 - - - balance of
Example 34 10 0.5 5 6 2 3 1 2 - - - balance of
Example 35 3 0.5 1 6 2 3 1 2 - - - balance of
Example 36 3 0.5 10 6 2 3 1 2 - - - Balance of
Example 37 3 0.5 5 1 2 3 1 2 - - - Balance of
Example 38 3 0.5 5 10 2 3 1 2 - - - Balance of
Example 39 3 0.5 5 6 0.3 3 1 2 - - - balance of
Example 40 3 0.5 5 6 10 3 1 2 - - - Balance of
EXAMPLE 41 3 0.5 5 6 2 1 1 2 - - - balance of
Example 42 3 0.5 5 6 2 10 1 2 - - - Balance of
Example 43 3 0.5 5 6 2 3 0.05 2 - - - Balance of
Example 44 3 0.5 5 6 2 3 5 2 - - - Balance of
Example 45 3 0.5 5 6 2 3 1 1 - - - Balance of
Example 46 3 0.5 5 6 2 3 1 10 - - - Balance of
Example 47 3 0.5 5 6 2 3 1 - 2 - - Balance of
Example 48 3 0.5 5 6 2 3 1 - - 2 - Balance of
Comparative example 32 3 0.5 5 6 2 3 1 - - - - Balance of
Comparative example 33 3 0.5 5 6 2 3 1 - - - 4 Balance of
ComparisonExample 34 - 0.5 5 6 2 3 1 2 - - - Balance of
Comparative example 35 13 0.5 5 6 2 3 1 2 - - - Balance of
comparative example 36 3 0.5 0.5 6 2 3 1 2 - - - Balance of
Comparative example 37 3 0.5 13 6 2 3 1 2 - - - balance of
Comparative example 38 3 0.5 5 - 2 3 1 2 - - - Balance of
comparative example 39 3 0.5 5 13 2 3 1 2 - - - Balance of
Comparative example 40 3 0.5 5 6 0 3 1 2 - - - Balance of
Comparative example 41 3 0.5 5 6 13 3 1 2 - - - Balance of
Comparative example 42 3 0.5 5 6 2 0 1 2 - - - Balance of
Comparative example 43 3 0.5 5 6 2 13 1 2 - - - Balance of
Comparative example 44 3 0.5 5 6 2 3 0 2 - - - Balance of
Comparative example 45 3 0.5 5 6 2 3 7 2 - - - Balance of
Comparative example 46 3 0.5 5 6 2 3 1 13 - - - Balance of
(A)：Cu(II)SO4
(B) The method comprises the following steps Ammonium fluoride
(C) The method comprises the following steps Nitric acid
(D) The method comprises the following steps Citric acid
(E) The method comprises the following steps Ammonium chloride
(F) The method comprises the following steps Ammonium sulfate
(G) The method comprises the following steps 5-methyltetrazole
(H) The method comprises the following steps Cis-cyclobutane-1, 2-dicarboxylic acid
(I) The method comprises the following steps Cis-1, 2,3, 4-cyclopentanetetracarboxylic dianhydride
(J) The method comprises the following steps Trans-cyclobutane-1, 2-dicarboxylic acid
(K) The method comprises the following steps Trans-4-cyclohexene-1, 2-dicarboxylic acid
(L): phthalic acid; benzene-1, 2-dicarboxylic acid
(M): terephthalic acid; benzene-1, 4-dicarboxylic acid
(N): malonic acid
(O): succinic acid
(P): glutaric acid
(Q): adipic acid
Test examples evaluation of etching Properties
Etching was performed using each of the etchant compositions of examples 1 to 48 and comparative examples 1 to 46. The temperature of the etchant composition during the etching process was set at around 30 c using a spray etch type test equipment (model: etcher (tft), SEMES co., Ltd.). The etching time varies depending on the etching temperature, however, etching is generally performed for 30 seconds to 80 seconds in the LCD etching process. A cross section of a profile of the titanium/copper bi-layer etched in the etching process was observed using SEM (product of Hitachi, ltd., model S-4700) during the etching process, and the results are shown in the following table 4, table 5, table 6, fig. 1, fig. 2, and fig. 3.
[ Table 4]
[ Table 5]
[ Table 6]
Non-etching: cu without etching non-pattern unit and without forming pattern
Etching profile defects: refers to the straightness defects and defects in the oblique plane of the Cu lines of the pattern unit in SEM measurement
As shown in tables 4 to 6, examples 1 to 48 exhibited superior properties in the number of processed plates and the etching profile, as compared to comparative examples 1 to 46.
Specifically, as shown in fig. 1, example 1 exhibited an excellent etching profile compared to comparative example 12 to which no inorganic salt (ammonium sulfate) was added.
As shown in fig. 2, example 17 showed an excellent etching profile compared to comparative example 27 in which no inorganic salt (ammonium sulfate) was added.
Further, as shown in fig. 3, example 32 shows an excellent etching profile compared to comparative example 42 to which an inorganic salt (ammonium sulfate) is not added.
When the etchant composition of the present invention is used to etch a copper-based metal layer, excellent etching profile and a large number of work sheets can be obtained.

Claims (7)

1. An etchant composition for copper-based metal layers comprising, relative to the total weight of the composition,
0.5 to 10% by weight of a copper compound;
0.01 to 2% by weight of a fluorine compound;
1 to 10% by weight of one or more types of inorganic acids selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and perchloric acid;
0.1 to 10% by weight of one or more types of chlorine compounds selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride, ammonium chloride, methanesulfonyl chloride, ethanesulfonyl chloride, chlorobenzenesulfonyl chloride, benzenesulfonyl chloride and chloroethanesulfonyl chloride;
1 to 10% by weight of one or more types of organic acids selected from the group consisting of acetic acid, butyric acid, citric 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, malic acid, tartaric acid, isocitric acid, propionic acid, iminodiacetic acid, and ethylenediaminetetraacetic acid, or a salt thereof;
0.1 to 10% by weight of one or more types of inorganic salts selected from the group consisting of ammonium sulfate, sodium sulfate, potassium sulfate, calcium sulfate, ammonium bisulfate, sodium bisulfate, potassium bisulfate, calcium hydrogen sulfate, ammonium nitrate, sodium nitrate, potassium nitrate and calcium nitrate;
0.01 to 5% by weight of a cyclic amine compound;
0.5 to 10% by weight of a chelating agent; and
The balance of water is added into the mixture,
Wherein the chelating agent is
1) A cis-dicarboxylic acid or a salt thereof,
2) One or more types selected from the group consisting of maleic acid, citraconic acid, phthalic acid, 1,2,4, 5-benzenetetracarboxylic acid, mellitic acid, 4-sulfophthalic acid, quinolinic acid, cis-5-norbornene-exo-2, 3-dicarboxylic acid, 1,2,3, 4-cyclobutanetetracarboxylic acid and cis, cis-1, 2,3, 4-cyclopentanetetracarboxylic acid, or a salt thereof, or
3) One or more types selected from the group consisting of malonic acid, succinic acid, and glutaric acid, or salts thereof.
2. The etchant composition for copper-based metal layers according to claim 1, wherein the chelating agent is
1) One or more types selected from the group consisting of: from cis-cyclobutane-1, 2-dicarboxylic acid, cis-1, 2,3, 4-cyclopentanetetracarboxylic dianhydride, benzene-1, 2-dicarboxylic acid, maleic anhydride, citraconic anhydride, 2, 3-dimethylmaleic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, phenylmaleic anhydride, 2,3-dihydro-1, 4-dithio [2,3-C ] furan-5,7-dione, phthalic anhydride, 4-methylphthalic anhydride, pyromellitic dianhydride, 3-oxabicyclo [3,1,0] -hexane-2, 4-dione, cis-1, 2,3, 4-cyclopentanetetracarboxylic dianhydride, cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride, cis-5-norbornene-exo-2, 3-dicarboxylic anhydride, cis-1, 2,3, 6-tetrahydrophthalic anhydride, maleic acid, citraconic acid, phthalic acid, 1,2,4, 5-benzenetetracarboxylic acid, mellitic acid, and 4-sulfophthalic acid; or a salt thereof,
2) One or more types selected from the group consisting of maleic acid, citraconic acid, phthalic acid, 1,2,4, 5-benzenetetracarboxylic acid, mellitic acid, 4-sulfophthalic acid, quinolinic acid, cis-5-norbornene-exo-2, 3-dicarboxylic acid, 1,2,3, 4-cyclobutanetetracarboxylic acid and cis, cis-1, 2,3, 4-cyclopentanetetracarboxylic acid, or a salt thereof, or
3) One or more types selected from the group consisting of malonic acid, succinic acid, and glutaric acid, or salts thereof.
3. The etchant composition for copper-based metal layers according to claim 1, wherein the copper-based metal layer is a double layer of titanium or a titanium alloy and copper or a copper alloy.
4. A method of manufacturing an array substrate for a liquid crystal display device, the method comprising,
a) Forming a gate line on a substrate;
b) Forming a gate insulating layer on the substrate including the gate line;
c) forming a semiconductor layer on the gate insulating layer;
d) Forming source and drain electrodes on the semiconductor layer; and
e) Forming a pixel electrode connected to the drain electrode,
Wherein the step a) or d) comprises forming a copper-based metal layer on the substrate or the semiconductor layer and etching the copper-based metal layer with the etchant composition of claim 1 to form a gate line, or source and drain electrodes.
5. The method of manufacturing an array substrate for a liquid crystal display device according to claim 4, wherein the array substrate for a liquid crystal display device is a thin film transistor array substrate.
6. the method of manufacturing an array substrate for a liquid crystal display device according to claim 4, wherein the copper-based metal layer is a double layer of titanium or a titanium alloy and copper or a copper alloy.
7. An array substrate for a liquid crystal display device, which is manufactured by the manufacturing method according to claim 4.
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