CN110484258B - Etchant composition for indium oxide layer - Google Patents
Etchant composition for indium oxide layer Download PDFInfo
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- CN110484258B CN110484258B CN201910679544.8A CN201910679544A CN110484258B CN 110484258 B CN110484258 B CN 110484258B CN 201910679544 A CN201910679544 A CN 201910679544A CN 110484258 B CN110484258 B CN 110484258B
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- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 80
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 238000005530 etching Methods 0.000 claims abstract description 49
- -1 nitrate compound Chemical class 0.000 claims abstract description 21
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 19
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 4
- TYHJXGDMRRJCRY-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) tin(4+) Chemical compound [O-2].[Zn+2].[Sn+4].[In+3] TYHJXGDMRRJCRY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 230000000873 masking effect Effects 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 16
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 124
- 230000000052 comparative effect Effects 0.000 description 23
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 230000003628 erosive effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
-
- 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
- H01L21/302—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
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Optics & Photonics (AREA)
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- Power Engineering (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Thin Film Transistor (AREA)
- Liquid Crystal (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Abstract
Disclosed are an etchant composition for etching an indium oxide layer, an etching method, a liquid crystal display array substrate using the same, and a method of manufacturing the same, the etchant composition including nitric acid or nitrous acid, a chlorine compound, a nitrate compound, and water.
Description
This application is a divisional application of the chinese invention patent application entitled "etchant composition for indium oxide layer, etching method, liquid crystal display array substrate using the same and manufacturing method thereof" filed on 4.2.2016 under the name of 201610079267.3.
Technical Field
The present invention relates to an etchant composition for etching an indium oxide layer, an etching method, and a liquid crystal display array substrate using the same and a method of manufacturing the same, and more particularly, to an etchant composition for etching an indium oxide layer, which includes nitric acid or nitrous acid, a chlorine compound, a nitrate compound, and water, and a liquid crystal display array substrate using the same and a method of manufacturing the same.
Background
Among flat panel displays, Liquid Crystal Display (LCD) devices have received attention due to their high resolution, clear image, low power consumption, and thin display screen. An electronic circuit that can be generally used for driving the LCD device is a Thin Film Transistor (TFT) circuit, and particularly, a TFT is formed for each pixel of the display screen. A TFT-LCD using a TFT as a switching element includes a TFT substrate disposed in a matrix, a color filter substrate disposed to face the substrate, and a liquid crystal material interposed between the two substrates. The method for manufacturing the TFT-LCD comprises the steps of preparing a TFT substrate, forming a color filter substrate, processing a liquid crystal box and processing a module. Therefore, in order to realize accurate and clear images, the fabrication of the TFT substrate and the color filter substrate is considered to be very important.
The LCD device includes a gate line or a scan signal line transmitting a scan signal, a data line or an image signal line transmitting an image signal, a TFT connected to the gate line and the data line, and a pixel electrode connected to the TFT.
The LCD device is manufactured as follows: forming a metal layer for gate and data lines on a substrate, etching the metal layer, forming a pixel electrode connected to the TFT, applying a photoresist, and forming a pattern. Thus, the gate line or the source/drain line connected to or exposed from the pixel electrode layer may be deformed during the patterning of the pixel electrode.
To solve this problem, the kind of material used for the pixel electrode must be different from the metal used for the gate electrode or the source/drain electrodes. Specifically, the material of the pixel electrode includes an indium oxide layer having optical transparency and high conductivity, such as a-ITO, IZO, IGZO, or ITZO.
Recently, the indium oxide layer is formed to have a finer pattern and to be thicker in order to realize a display device having high resolution and fast response speed.
Korean patent application publication No.10-2012-0093499 discloses an etchant composition for etching an indium oxide layer, but has problems in that sulfuric acid, which is harmful to the environment, is used, and moreover, a thick indium oxide layer cannot be etched.
[ list of references ]
[ patent document ]
Patent documents: korean patent application publication No.10-2012 and 0093499
Disclosure of Invention
Accordingly, it is an object of the present invention to provide an etchant composition for etching an indium oxide layer that can etch an indium oxide layer while minimizing damage to a lower metal layer disposed below the indium oxide layer.
It is another object of the present invention to provide an etchant composition for etching an indium oxide layer, which has a high ability to etch a thick indium oxide layer, thus enabling formation of a fine pattern, and which can also reduce an undercut distance of the indium oxide layer, thereby preventing line loss due to over-etching of the pattern.
In order to achieve the above object, the present invention provides an etchant composition for etching an indium oxide layer, comprising: based on the total weight thereof, 5 to 12 wt% of nitric acid or nitrous acid, 0.01 to 5 wt% of a chlorine compound, 0.01 to 3 wt% of a nitrate compound, and the balance of water, such that the total weight of the etchant composition is 100 wt%.
In addition, the present invention provides a method of etching an indium oxide layer, the method comprising: (1) forming an indium oxide layer on a substrate, (2) selectively leaving a photosensitive material on the indium oxide layer, and (3) etching the indium oxide layer using the etchant composition of the present invention.
In addition, the present invention provides a method of manufacturing an array substrate for a liquid crystal display, the method including: (1) forming a gate line on a substrate, (2) forming a gate insulating layer on the substrate including the gate line, and (3) forming an oxide semiconductor layer on the gate insulating layer, (4) forming a source electrode and a drain electrode on the oxide semiconductor layer, and (5) forming a pixel electrode connected to the drain electrode, wherein (5) includes forming an indium oxide layer and etching the indium oxide layer with an etchant composition to form the pixel electrode, and the etchant composition is the etchant composition of the present invention.
In addition, the invention provides the liquid crystal display array substrate manufactured by the method.
According to the present invention, an etchant composition for etching an indium oxide layer has high power to etch a thick indium oxide layer, thereby forming a fine pattern, and effectively preventing loss of lines by suppressing over-etching of the indium oxide layer.
Further, according to the present invention, the etchant composition for etching an indium oxide layer can etch an indium oxide layer while minimizing damage to a lower metal layer under the indium oxide layer.
Drawings
The above and other objects, features and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a Scanning Electron Microscope (SEM) image showing the undercut distance of an indium oxide layer;
FIG. 2 is an SEM image showing no residue from the indium oxide layer;
FIG. 3 is an SEM image showing residue generated from an indium oxide layer;
FIG. 4 is an SEM image showing no damage to the aluminum/molybdenum layer below the indium oxide layer; and
fig. 5 is an SEM image showing damage to the aluminum/molybdenum layer below the indium oxide layer.
Detailed Description
Hereinafter, a detailed description of the present invention will be given.
The present invention provides an etchant composition for etching an indium oxide layer, which includes, based on the total weight of the etchant composition, 5 to 12 wt% of nitric acid or nitrous acid, 0.01 to 5 wt% of a chlorine compound, 0.01 to 3 wt% of a nitrate compound, and the balance of water, such that the total weight of the etchant composition is 100 wt%.
Although the indium oxide layer conventionally used for the pixel electrode in the liquid crystal display has
Or smaller, but it needs to be made thicker in order to realize a liquid crystal display having a fast response speed and high resolution. Therefore, the thickness of the indium oxide layer must be set to
Or thicker.
As the indium oxide layer becomes thicker, a period of time required to etch the indium oxide layer so as to form the pixel electrode increases. Thus, the amount of etching increases not only in the longitudinal direction but also in the lateral direction, undesirably causing over-etching, making it impossible to etch a fine pattern ensuring high resolution. Therefore, it is difficult to form a fine pixel electrode.
With the object of solving this problem, the etchant composition for etching an indium oxide layer according to the present invention contains a nitrate compound.
In particular, the etchant composition according to the present invention may exhibit the ability to etch a thicker indium oxide layer, thereby reducing the degree of undercut of the indium oxide layer, thereby preventing over-etching, and making it possible to etch fine patterns, thereby realizing a liquid crystal display having high resolution.
In addition, since the nitrate compound is included in the etchant composition, damage to the lower metal layer may be minimized when etching the indium oxide layer.
The indium oxide layer etched using the etchant composition according to the present invention has a thickness of 500 to
And preferably 900 to
Further, the indium oxide layer includes at least one selected from the group consisting of an Indium Tin Oxide (ITO) layer, an Indium Zinc Oxide (IZO) layer, an Indium Tin Zinc Oxide (ITZO) layer, and an Indium Gallium Zinc Oxide (IGZO) layer.
The kind of the lower layer below the indium oxide layer is not particularly limited, but may include a single layer including a molybdenum-based metal layer or an aluminum-based metal layer, or a plurality of layers including the single layer.
The following is a description of the individual components of the etchant composition according to the present invention.
In the etchant composition according to the present invention, nitric acid (HNO)3) Or nitrous acid (HNO)2) Which acts as the primary etchant for the indium oxide layer by oxidation and displacement reactions.
The amount of nitric acid or nitrous acid is 5 to 12 wt%, and preferably 7 to 10 wt%, based on the total weight of the etchant composition.
If the amount of nitric acid or nitrous acid is less than 5 wt%, the indium oxide layer cannot be etched effectively, undesirably increasing the etching time and generating residues and etching defects. On the other hand, if the amount of nitric acid or nitrous acid exceeds 12 wt%, a larger amount of waste liquid is generated due to an increase in the amount of nitrogen, undesirably increasing waste liquid disposal costs and environmental pollution treatment costs.
In the etchant composition according to the present invention, the chlorine compound functions as an auxiliary etchant for the indium oxide layer by substitution. When the indium oxide layer is etched, a large amount of etching residues are generated, and the chlorine compound is responsible for suppressing the generation of the residues.
The chlorine compound includes at least one selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride, and ammonium chloride.
The chlorine compound is used in an amount of 0.01 to 5 wt%, and preferably 1 to 3 wt%, based on the total weight of the etchant composition.
If the amount of the chlorine compound is less than 0.01 wt%, the indium oxide layer cannot be effectively etched, undesirably increasing the etching time and generating residues and etching defects. On the other hand, if the amount of the chlorine compound exceeds 5 wt%, the etching rate excessively increases to cause over-etching, thereby failing to sufficiently form an area necessary for driving the pixel electrode.
In the etchant composition according to the present invention, the nitrate compound functions to prevent corrosion generated by exposure of the surrounding portion of the contact hole in the lower metal layer below the indium oxide layer to the etchant composition.
In addition, when the etching has 500 to
And preferably 900 to
The nitrate compound also serves to prevent excessive undercutting of the indium oxide layer in response to increased etch times with a thick indium oxide layer.
The nitrate compound includes at least one selected from the group consisting of sodium nitrate, ammonium nitrate and potassium nitrate.
The nitrate compound is used in an amount of 0.01 to 3 wt%, and preferably 1 to 2.5 wt%, based on the total weight of the etchant composition.
If the amount of the nitrate compound is less than 0.01 wt%, corrosion cannot be sufficiently prevented, undesirably causing damage to the lower metal layer and increasing undercut of the indium oxide layer, thereby making it difficult to form a finely patterned indium oxide layer. On the other hand, if the amount of the nitrate compound exceeds 3 wt%, it may function to prevent corrosion, but may reduce the etching rate of the indium oxide layer and may thus generate residue.
In the etchant composition of the present invention, the amount of water used is such that the total weight of the etchant composition is 100 wt%. The water is not particularly limited, but preferably includes deionized water. Particularly useful is deionized water having a resistivity of 18M Ω cm or more, the resistivity indicating the degree of ion removal from the water.
The etchant composition according to the present invention may further include at least one selected from the group consisting of a masking agent and an anti-corrosion agent. The additive is not limited thereto, and various additives known in the art may be selectively added in order to more effectively exhibit the effects of the present invention.
The components of the etchant composition according to the present invention may be prepared using generally known methods, and may have a purity suitable for semiconductor processing.
In addition, the present invention provides a method of etching an indium oxide layer, the method comprising: (1) forming an indium oxide layer on a substrate, (2) selectively leaving a photosensitive material on the indium oxide layer, and (3) etching the indium oxide layer using the etchant composition of the present invention.
In the etching method according to the present invention, the photosensitive material is preferably a general photoresist material, and can be selectively left by general exposure and development.
The indium oxide layer has a thickness of 500 to
And preferably 900 to
In the form of a single layer of thickness.
The indium oxide layer includes at least one selected from the group consisting of an Indium Tin Oxide (ITO) layer, an Indium Zinc Oxide (IZO) layer, an Indium Tin Zinc Oxide (ITZO) layer, and an Indium Gallium Zinc Oxide (IGZO) layer.
In addition, the present invention provides a method of manufacturing an array substrate for a liquid crystal display, the method including: (1) forming a gate line on a substrate, (2) forming a gate insulating layer on the substrate including the gate line, (3) forming an oxide semiconductor layer on the gate insulating layer, (4) forming a source electrode and a drain electrode on the oxide semiconductor layer, and (5) forming a pixel electrode connected to the drain electrode, wherein (5) includes forming an indium oxide layer and etching the indium oxide layer with an etchant composition, thereby forming the pixel electrode, and the etchant composition is the etchant composition described above.
The indium oxide layer has a thickness of 500 to
And preferably 900 to
In the form of a single layer of thickness.
The indium oxide layer includes at least one selected from the group consisting of an Indium Tin Oxide (ITO) layer, an Indium Zinc Oxide (IZO) layer, an Indium Tin Zinc Oxide (ITZO) layer, and an Indium Gallium Zinc Oxide (IGZO) layer.
In the above method (5), the pixel electrode may be formed by etching the indium oxide layer using the etchant composition of the present invention.
More specifically, with the etchant composition according to the present invention, the photoresist having a pattern of 500 to 500 can be etched in a fine pattern without excessive undercut
And preferably 900 to
Indium oxide layer of thickness for realizing rapid response speed and high resolutionThereby forming a pixel electrode achieving high resolution.
When the indium oxide layer is etched using the etchant composition of the present invention, damage to a lower metal layer under the indium oxide layer can be prevented, thereby forming a pixel electrode without damaging the lower metal layer.
The array substrate of the liquid crystal display device may be a Thin Film Transistor (TFT) array substrate.
In addition, the invention provides the array substrate of the liquid crystal display manufactured by the method.
The array substrate includes a pixel electrode formed by etching using the etchant composition according to the present invention.
In addition, the present invention may provide an Organic Light Emitting Diode (OLED), a Touch Screen (TS), or other electronic devices manufactured using the above etchant composition, in addition to the array substrate of the present invention.
Therefore, the following examples are merely presented for illustration and should not be construed as limiting the present invention, and may be appropriately modified or changed by those skilled in the art within the scope of the present invention.
<Preparation of etchant composition for etching indium oxide layer>
Examples 1 to 4 and comparative examples 1 to 7
The etchant compositions of examples 1 to 4 and comparative examples 1 to 7 were prepared using the components in the amounts shown in table 1 below, and the amount of water used was such that the total weight of the etchant compositions was 100 wt%.
[ Table 1]
(unit: wt%)
| Nitric acid | Sodium chloride | Sodium nitrate | Potassium nitrate | Potassium sulfate | Ammonium acetate | |
| Example 1 | 8.5 | 3 | 2 | - | - | - |
| Example 2 | 8.5 | 3 | - | 2 | - | - |
| Example 3 | 8.5 | 3 | 0.5 | - | - | - |
| Example 4 | 8.5 | 3 | 3 | - | - | - |
| Comparative example 1 | 7 | 1 | - | - | - | - |
| Comparative example 2 | 8.5 | 3 | - | - | - | - |
| Comparative example 3 | 8.5 | 3 | - | - | 2 | - |
| Comparative example 4 | 8.5 | 3 | - | - | - | 2 |
| Comparative example 5 | 14 | 3 | 2 | - | - | - |
| Comparative example 6 | 8.5 | 7 | 2 | - | - | - |
| Comparative example 7 | 8.5 | 3 | 5 | - | - | - |
Test example 1: evaluation of Properties of etchant composition for etching indium oxide layer
On a glass substrate (100mm x 100mm), an aluminum/molybdenum layer is deposited to form source/drain electrodes, and then silicon is formed on the aluminum/molybdenum layer and holes are formed therein, thereby exposing aluminum/molybdenum, which is a metal layer of the source/drain electrodes. Thereafter, an ITO layer is deposited to a thickness
And then, photolithography was performed to form a photoresist having a predetermined pattern on the substrate, and then the ITO layer was etched using each of the etchant compositions of examples 1 to 4 and comparative examples 1 to 7。
During the etching process, a spray etcher (tft), manufactured by SEMES) was used, and the temperature of the etchant composition was set to about 40 ℃. In addition, the appropriate temperature is varied as needed depending on other processing conditions and other factors. The etching time varies depending on the etching temperature, but is set in the range of about 50 to 120 seconds during LCD etching.
The cross-sectional profile of the ITO layer etched during etching was observed by SEM (S-4700, manufactured by HITACHI), and undercut, residue generation and erosion of the lower metal (Al/Mo) were observed, and evaluated based on the following evaluation criteria. The results are shown in table 2 below.
< undercut distance >
Very good: less than 0.2 μm (Excellent)
O: 0.2 to less than 0.5 μm (good)
X: 0.5 μm or more or not etched (poor)
< residue Generation >
O: without residue (fig. 2)
X: producing residues (FIG. 3)
< attack on underlayer (Al/Mo) >
O: non-erosion (fig. 4)
X: erosion (fig. 5)
[ Table 2]
| Side etching (mum) | Residue of rice | Erosion of underlying layers | |
| Example 1 | ◎ | ○ | ○ |
| Example 2 | ○ | ○ | ○ |
| Example 3 | ○ | ○ | ○ |
| Example 4 | ○ | ○ | ○ |
| Comparative example 1 | × | × | × |
| Comparative example 2 | ○ | ○ | × |
| Comparative example 3 | × | ○ | × |
| Comparative example 4 | × | ○ | × |
| Comparative example 5 | × | ○ | ○ |
| Comparative example 6 | × | ○ | ○ |
| Comparative example 7 | ○ | × | ○ |
As is apparent from the results of table 2, the etchant compositions of examples 1 to 4, which used the nitrate compound in an amount of 0.01 to 3 wt% based on the total weight of the etchant composition, observed that undercut was less than 0.2 μm, and neither residue nor erosion of the lower layer occurred.
However, in the etchant composition of comparative example 1 containing no nitrate compound, excessive undercut was generated, and residue and erosion of the lower layer were observed, and erosion of the lower layer was observed in the etchant composition of comparative example 2.
Further, in the etchant compositions of comparative examples 3 and 4, which respectively include potassium sulfate and ammonium acetate instead of the nitrate compound, no residue was generated, but excessive undercut and attack of the lower layer were observed.
In the etchant composition of comparative example 5 using an amount of nitric acid exceeding 12 wt% based on the total weight of the etchant composition and in the etchant composition of comparative example 6 using an amount of chlorine compound exceeding 5 wt%, neither residue nor erosion of the lower layer was observed, but excessive undercut was generated.
Further, in the etchant composition of comparative example 7 in which the nitrate compound was used in an amount exceeding 3 wt% based on the total weight of the etchant composition, undercut was limited and the lower layer was not eroded, but a residue was generated.
Therefore, the etchant composition according to the present invention, which includes the nitrate compound in an amount of 0.01 to 3 wt% based on the total weight of the etchant composition, has high ability to etch a thick indium oxide layer, and is capable of etching the indium oxide layer without damaging an underlying layer disposed under the indium oxide layer.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims (4)
1. An etchant composition for etching an indium oxide layer comprising: 5 to 12 wt% of nitric acid or nitrous acid, 0.01 to 5 wt% of a chlorine compound, 1 to 2.5 wt% of a nitrate compound, and the balance water, based on the total weight of the etchant composition, such that the total weight of the etchant composition is 100 wt%,
wherein the chlorine compound is sodium chloride and the chlorine compound is sodium chloride,
wherein the nitrate compound is sodium nitrate, and
wherein the undercut distance of the indium oxide layer is less than 0.5 μm.
2. The etchant composition of claim 1, wherein the indium oxide layer comprises at least one selected from the group consisting of an indium tin oxide layer, an indium zinc oxide layer, an indium tin zinc oxide layer, and an indium gallium zinc oxide layer.
3. The etchant composition of claim 1 wherein the indium oxide layer has a thickness of 500 to
Is measured.
4. The etchant composition of claim 1, further comprising at least one selected from the group consisting of a masking agent and an anti-corrosion agent.
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| CN1971351A (en) * | 2005-11-22 | 2007-05-30 | 东进世美肯株式会社 | Etching composition for ito |
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| JPH02111886A (en) * | 1988-10-18 | 1990-04-24 | Sumitomo Special Metals Co Ltd | Etching solution for partially al clad sheet for lead frame |
| JP2002184748A (en) * | 2000-12-12 | 2002-06-28 | Matsushita Electric Ind Co Ltd | Etching liquid and etching method using it |
| KR101294968B1 (en) * | 2006-11-20 | 2013-08-09 | 동우 화인켐 주식회사 | Etching solution composition and method of etching using the etching solution composition |
| KR20090082772A (en) * | 2008-01-28 | 2009-07-31 | 주식회사 동진쎄미켐 | Etchant composition for indium tin oxide layer and etching method using the same |
| JP5767796B2 (en) * | 2010-09-28 | 2015-08-19 | 林純薬工業株式会社 | Etching solution composition and etching method |
| KR101774484B1 (en) | 2011-02-15 | 2017-09-05 | 삼성디스플레이 주식회사 | Non-halogenated etchant for etching an indium oxide layer and method of manufacturing a display substrate using the non-halogenated etchant |
| KR20130084717A (en) * | 2012-01-18 | 2013-07-26 | 솔브레인 주식회사 | Etchant composition and method of manufacturing a display substrate using the etchant composition |
| CN102732252A (en) * | 2012-06-21 | 2012-10-17 | 江阴润玛电子材料股份有限公司 | Novel aqua regia system ITO (indium tin oxide) etching solution and its preparation method |
| CN102732253A (en) * | 2012-06-30 | 2012-10-17 | 江阴润玛电子材料股份有限公司 | Ferric trichloride ITO etching solution and its preparation method |
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| KR20140086666A (en) * | 2012-12-28 | 2014-07-08 | 동우 화인켐 주식회사 | Etchant composition for metal oxide layer |
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