CN110484258A - Etching agent composite for indium oxide layer - Google Patents
Etching agent composite for indium oxide layer Download PDFInfo
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- CN110484258A CN110484258A CN201910679544.8A CN201910679544A CN110484258A CN 110484258 A CN110484258 A CN 110484258A CN 201910679544 A CN201910679544 A CN 201910679544A CN 110484258 A CN110484258 A CN 110484258A
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- China
- Prior art keywords
- indium oxide
- oxide layer
- etching agent
- agent composite
- etching
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- 238000005530 etching Methods 0.000 title claims abstract description 98
- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 74
- 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 74
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 63
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 18
- -1 nitrate compound Chemical class 0.000 claims abstract description 17
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052738 indium Inorganic materials 0.000 claims description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-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
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 claims 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 28
- 238000000034 method Methods 0.000 abstract description 18
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 125
- 230000003628 erosive effect Effects 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 22
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 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
- 239000004411 aluminium Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 230000000694 effects Effects 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
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 3
- 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
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 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
- 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006073 displacement reaction Methods 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
- 238000003384 imaging method Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture 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
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000001259 photo etching Methods 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
- 230000008054 signal transmission Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- 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)
- Mathematical Physics (AREA)
- Power Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Optics & Photonics (AREA)
- Thin Film Transistor (AREA)
- Liquid Crystal (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Abstract
The etching agent composite for etching indium oxide layer is disclosed, engraving method, using their LCD (Liquid Crystal Display) array substrate and its manufacturing method, the etching agent composite includes nitric acid or nitrous acid, chlorine compound, nitrate compound and water.
Description
The application be submitted on 2 4th, 2016 application No. is 201610079267.3 it is entitled " for indium oxide
The etching agent composite of layer, engraving method uses their LCD (Liquid Crystal Display) array substrate and its manufacturing method " Chinese invention
The divisional application of patent application.
Technical field
The present invention relates to the etching agent composite for etching indium oxide layer, engraving method, and the liquid crystal using them
Show device array substrate and its manufacturing method, more specifically to including nitric acid or nitrous acid, chlorine compound, nitrate chemical combination
Object and water for etching indium oxide layer etching agent composite, and LCD (Liquid Crystal Display) array substrate and its manufacture using them
Method.
Background technique
Among flat-panel monitor, liquid crystal display (LCD) device since its high resolution, image clearly, power consumption are low and
Display screen is thin to receive attention.It usually can be used as driving the electronic circuit of LCD device being thin film transistor (TFT) (TFT) circuit, especially
It is that TFT is formed to each pixel of display screen.It include the TFT being arranged in matrix using TFT as the TFT-LCD of switch element
Substrate is arranged to the colored filter substrate towards the substrate and the liquid crystal material between above-mentioned two substrate.Production
The method of TFT-LCD includes preparation TFT substrate, forms colored filter substrate, liquid crystal cell processing and module processing.Therefore, it is
It realizes accurately and clearly image, the production of the TFT substrate and the colored filter substrate is considered extremely important
's.
The LCD device includes the data line for transmitting the grid line or scan signal line, image signal transmission of scanning signal
Or image signal line, the TFT being connect with the grid line and data line and the pixel electrode being connect with the TFT.
The LCD device manufactures as follows: forming the metal layer for being used for grid line and data line on substrate, etches the gold
Belong to layer, form the pixel electrode connecting with TFT, applies photoresist, and form pattern.Thus, it is connect with the pixel electrode layer
Or the exposed grid line or source/drain polar curve may deformation during the pixel electrode forms pattern.
In order to solve this problem, for the type of the material of pixel electrode necessarily different from for the grid or source/
The metal of drain electrode.Specifically, the material of the pixel electrode includes the indium oxide layer with optical clarity and high conductivity,
Such as a-ITO, IZO, IGZO or ITZO.
Recently, the indium oxide layer is formed with finer pattern and thicker, to realize with high-resolution
The display device of rate and rapid response speed.
Korean patent application publication No.10-2012-0093499 discloses the etchant combination for etching indium oxide layer
Object, there is problems in that the harmful sulfuric acid of environment has been used, moreover, thick indium oxide layer cannot be etched.
[reference listing]
[patent document]
Patent document: Korean patent application publication No.10-2012-0093499
Summary of the invention
Therefore, the purpose of the present invention is to provide the etching agent composites for etching indium oxide layer, can etch oxidation
Indium layer minimizes the damage to the lower metal layer being arranged under the indium oxide layer simultaneously.
It is a further object to provide the etching agent composite for etching indium oxide layer, has and etch thick oxygen
Change the ability of indium layer, therefore is capable of forming fine pattern, and its lateral erosion distance that can also reduce the indium oxide layer, from
And prevent lines caused by the pattern as described in overetch from losing.
To achieve the goals above, the present invention provides the etching agent composites for etching indium oxide layer, comprising: is based on
Its total weight, 5 to 12wt% nitric acid or nitrous acid, 0.01 to 5wt% chlorine compound, 0.01 to 3wt% nitric acid salinization
The water for closing object and surplus, so that the total weight of the etching agent composite is 100wt%.
In addition, the present invention provides the methods of etching indium oxide layer, which comprises (1) form oxidation on substrate
Indium layer, (2) selectively leave light-sensitive material in the indium oxide layer, and (3) are lost using etching agent composite of the invention
Carve the indium oxide layer.
In addition, the present invention provides the methods of the array substrate of manufacture liquid crystal display, which comprises (1) in base
Grid line is formed on plate, (2) form gate insulating layer, and (3) in the gate insulator on the substrate for including the grid line
Oxide semiconductor layer is formed on layer, (4) form source electrode and drain electrode, and (5) on the oxide semiconductor layer
The pixel electrode connecting with the drain electrode is formed, wherein (5) include forming indium oxide layer and losing using etching agent composite
The indium oxide layer is carved, to form the pixel electrode, and the etching agent composite is etchant combination of the invention
Object.
In addition, the present invention provides the LCD (Liquid Crystal Display) array substrates manufactured by the above method.
According to the present invention, the etching agent composite for etching indium oxide layer has the ability for etching thick indium oxide layer,
To form fine pattern, and by inhibiting the overetch of the indium oxide layer to effectively prevent the loss of lines.
In addition, according to the present invention, the etchable indium oxide layer of etching agent composite for etching indium oxide layer is simultaneously
Minimize the damage to the lower metal layer under the indium oxide layer.
Detailed description of the invention
Above and other objects, features and advantages of the invention will be from following detailed description of the accompanying drawings more clearly
Understand, in which:
Fig. 1 is scanning electron microscope (SEM) image, shows the lateral erosion distance of indium oxide layer；
Fig. 2 is SEM image, shows residue not from indium oxide layer；
Fig. 3 is SEM image, shows the residue generated from indium oxide layer；
Fig. 4 is SEM image, is shown not to aluminium/molybdenum layer damage under indium oxide layer；With
Fig. 5 is SEM image, is shown to aluminium/molybdenum layer damage under indium oxide layer.
Specific embodiment
Hereinafter, it detailed description of the present invention will be given.
The invention proposes the etching agent composites for etching indium oxide layer comprising, it is based on the etchant combination
The total weight of object, 5 to 12wt% nitric acid or nitrous acid, 0.01 to 5wt% chlorine compound, 0.01 to 3wt% nitrate
The water of compound and surplus, so that the total weight of the etching agent composite is 100wt%.
Although the indium oxide layer conventionally used for pixel electrode in liquid crystal display hasOr smaller thickness, but
In order to realize with rapid response speed and high-resolution liquid crystal display, it needs to become thicker.Therefore, the indium oxide
The thickness of layer must be set asOr it is thicker.
As indium oxide layer thickens, the indium oxide layer is etched to form the period required for pixel electrode and to increase.
Thus, not only increase in longitudinal direction but also in lateral etch quantity, undesirably results in overetch, making it impossible to etch ensures
High-resolution fine pattern.Accordingly, it is difficult to form fine pixel electrode.
With the target for solving this problem, the etching agent composite according to the present invention for etching indium oxide layer contains
Nitrate compound.
Specifically, etching agent composite according to the present invention can show the ability for etching thicker indium oxide layer, by
This reduces the lateral erosion degree of the indium oxide layer, to prevent overetch, and makes it possible to etch fine pattern, to realize
With high-resolution liquid crystal display.
In addition, because in the etching agent composite including the nitrate compound, it can be with when etching indium oxide layer
Minimize the damage to lower metal layer.
Using etching agent composite according to the present invention etching indium oxide layer have 500 toThickness, and
It is preferred that 900 to
In addition, the indium oxide layer includes selected from by tin indium oxide (ITO) layer, indium zinc oxide (IZO) layer, indium tin zinc oxide
(ITZO) at least one of layer and the composed group of indium gallium zinc (IGZO) layer.
Lower layer's type under the indium oxide layer is not particularly limited, but may include single layer, including molybdenum base gold
Belong to layer or aluminium based metal layer, or the multilayer including the single layer.
Here is the explanation to each component of etching agent composite according to the present invention.
In etching agent composite according to the present invention, nitric acid (HNO3) or nitrous acid (HNO2) anti-by oxidation and displacement
Using the primary etchant for making indium oxide layer.
Based on the etching agent composite total weight, the dosage of nitric acid or nitrous acid is 5 to 12wt%, and preferably 7 to
10wt%.
If the amount of nitric acid or nitrous acid is less than 5wt%, indium oxide layer cannot be effectively etched, erosion is undesirably increased
It carves the time and generates residue and etching defect.On the other hand, if the amount of nitric acid or nitrous acid is more than 12wt%, due to nitrogen quantity
Increase causes to generate larger amount of waste liquid, undesirably increases waste liquid cost of disposal and environmental pollution treatment cost.
In etching agent composite according to the present invention, the chlorine compound plays the auxiliary of the indium oxide layer by replacing
Help the effect of etchant.When etching indium oxide layer, a large amount of etch residue is generated, the chlorine compound is responsible for inhibiting residue
It generates.
The chlorine compound includes at least one in the group as composed by hydrochloric acid, sodium chloride, potassium chloride and ammonium chloride
Kind.
Based on the total weight of the etching agent composite, the dosage of the chlorine compound is 0.01 to 5wt%, and preferably 1
To 3wt%.
If the amount of the chlorine compound is less than 0.01wt%, indium oxide layer cannot be effectively etched, is undesirably increased
Etching period simultaneously generates residue and etching defect.On the other hand, if the amount of the chlorine compound is more than 5wt%, speed is etched
Rate is excessively increased, and so as to cause overetch, thus not sufficiently forms the necessary area of driving pixel electrode.
In etching agent composite according to the present invention, the nitrate compound, which has played, to be prevented in the indium oxide layer
Under lower metal layer in peripheral part of contact hole be exposed to the etching agent composite and the effect of corrosion that generates.
In addition, when etching have 500 toAnd preferably 900 toIt is described when the indium oxide layer of thickness
Nitrate compound also acts as the effect for preventing the indium oxide layer in response to the increased excessive lateral erosion of etching period.
The nitrate compound includes at least one in the group as composed by sodium nitrate, ammonium nitrate and potassium nitrate
Kind.
Based on the total weight of the etching agent composite, the dosage of the nitrate compound is 0.01 to 3wt%, and excellent
It selects 1 to 2.5wt%.
If the amount of the nitrate compound is less than 0.01wt%, it cannot be substantially prevented from corrosion, under undesirably causing
The damage of portion's metal layer and the lateral erosion for increasing indium oxide layer, so that being difficult to form the indium oxide layer of fine pattern.Another party
Face, if the amount of the nitrate compound is more than 3wt%, it can play the role of preventing corrosion, but can reduce oxygen
Change the etch-rate of indium layer and can thus generate residue.
In etching agent composite of the invention, the water used will make the total weight of the etching agent composite be
100wt%.The water is not particularly limited, it is preferred that including deionized water.It is especially useful that resistivity is 18M Ω
Cm or higher deionized water, resistivity show from the water except deionized degree.
Etching agent composite according to the present invention can also include in the group as composed by screening agent and corrosion inhibitor
At least one.The additive is without being limited thereto, and in order to more effectively show effect of the invention, the property of can choose addition
Various additives known in the art.
The component of etching agent composite according to the present invention can use commonly known method preparation, and can have
It is suitable for the purity of semiconductor machining.
In addition, the invention proposes the methods of etching indium oxide layer, which comprises (1) form oxidation on substrate
Indium layer, (2) selectively leave light-sensitive material in the indium oxide layer, and (3) are etched using etching agent composite of the invention
The indium oxide layer.
In engraving method according to the present invention, the light-sensitive material is preferably common Other substrate materials, and can be with
It is selectively left by common exposure and imaging.
The indium oxide layer with have 500 toAnd preferably 900 toThe form of the single layer of thickness
It provides.
The indium oxide layer includes selected from by tin indium oxide (ITO) layer, indium zinc oxide (IZO) layer, indium tin zinc oxide
(ITZO) at least one of layer and the composed group of indium gallium zinc (IGZO) layer.
In addition, the invention proposes the methods of the array substrate of manufacture liquid crystal display, which comprises (1) in base
Grid line is formed on plate, (2) form gate insulating layer on the substrate for including the grid line, and (3) are in the gate insulating layer
Upper formation oxide semiconductor layer, (4) form source electrode and drain electrode, and (5) shape on the oxide semiconductor layer
At the pixel electrode being connect with the drain electrode, wherein (5) include forming indium oxide layer and being etched using etching agent composite
The indium oxide layer, to form the pixel electrode, and the etching agent composite is above-described etchant combination
Object.
The indium oxide layer with have 500 toAnd preferably 900 toThe form of the single layer of thickness
It provides.
The indium oxide layer includes selected from by tin indium oxide (ITO) layer, indium zinc oxide (IZO) layer, indium tin zinc oxide
(ITZO) at least one of layer and the composed group of indium gallium zinc (IGZO) layer.
In (5) of the above method, the pixel electrode can be by etching institute using etching agent composite of the invention
Indium oxide layer is stated to be formed.
It more specifically, can be with fine pattern and without excessive side using etching agent composite according to the present invention
The form etching of erosion is described have 500 toAnd preferably 900 toThe indium oxide layer of thickness, the oxidation
Indium layer is consequently formed for realizing with rapid response speed and high-resolution liquid crystal display and reaches high-resolution pixel
Electrode.
When etching indium oxide layer using etching agent composite of the invention, can prevent under the indium oxide layer
The damage of lower metal layer, to form pixel electrode in the case where not damaging lower metal layer.
The array substrate of liquid crystal display device can be thin film transistor (TFT) (TFT) array substrate.
In addition, the invention proposes the array substrates of the liquid crystal display manufactured by the above method.
The array substrate includes the pixel electrode by being formed using etching agent composite according to the present invention etching.
In addition, the present invention, which can also provide, utilizes above-mentioned etching agent composite system other than array substrate of the invention
Organic Light Emitting Diode (OLED), touch screen (TS) or other electronic devices made.
Therefore, only propose that following embodiment is illustrated but is not necessarily to be construed as the limitation present invention, and can be by this
Field technical staff is suitably modified within the scope of the invention or changes.
<for etching the preparation of the etching agent composite of indium oxide layer>
Embodiment 1 to 4 and comparative example 1 to 7
The etching agent composite of embodiment 1 to 4 and comparative example 1 to 7 is prepared using the component of amount shown in following table 1,
And the water used makes the total weight of the etching agent composite be 100wt%.
[table 1]
(unit: wt%)
| Nitric acid | Sodium chloride | Sodium nitrate | Potassium nitrate | Potassium sulfate | Ammonium acetate | |
| Embodiment 1 | 8.5 | 3 | 2 | - | - | - |
| Embodiment 2 | 8.5 | 3 | - | 2 | - | - |
| Embodiment 3 | 8.5 | 3 | 0.5 | - | - | - |
| Embodiment 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: for etching the properties evaluations of the etching agent composite of indium oxide layer
On glass substrate (100mm x 100mm), deposition of aluminum/molybdenum layer is to form source/drain, then in the aluminium/molybdenum
Silicon is formed on layer and forms hole wherein, is thus exposed aluminium/molybdenum, is the metal layer of the source/drain.Later, ITO layer is sunk
Product arrives thicknessThen photoetching is carried out, so that photoresist on the substrate with predetermined pattern is formed, it is then sharp
The ITO layer is etched with each etching agent composite of embodiment 1 to 4 and comparative example 1 to 7.
In etching process, using spraying etching machine (ETCHER (TFT), SEMES manufacture), and the etchant combination
The temperature setting of object is to about 40 DEG C.In addition, depend on other processing conditions and other factors, temperature appropriate as needed and
Become.Etching period depends on etch temperature and becomes, but is arranged in the range of about 50 to 120 seconds in LCD etching process.
Using the cross-sectional profiles of the ITO layer etched in SEM (S-4700, HITACHI are manufactured) observation etching process, and see
Lateral erosion, residue generation and the erosion to lower metal (Al/Mo) are examined, is evaluated based on following evaluation criterion.Exist as the result is shown
In following table 2.
<lateral erosion distance>
◎: less than 0.2 μm (outstanding)
Zero: 0.2 to less than 0.5 μm (good)
It X:0.5 μm or higher or does not etch (poor)
<residue generation>
Zero: not having residue (Fig. 2)
X: it generates residue (Fig. 3)
<erosion (Al/Mo) to lower layer>
Zero: non-corrosive (Fig. 4)
X: it corrodes (Fig. 5)
[table 2]
| Lateral erosion (μm) | Residue | Erosion to lower layer | |
| Embodiment 1 | ◎ | ○ | ○ |
| Embodiment 2 | ○ | ○ | ○ |
| Embodiment 3 | ○ | ○ | ○ |
| Embodiment 4 | ○ | ○ | ○ |
| Comparative example 1 | × | × | × |
| Comparative example 2 | ○ | ○ | × |
| Comparative example 3 | × | ○ | × |
| Comparative example 4 | × | ○ | × |
| Comparative example 5 | × | ○ | ○ |
| Comparative example 6 | × | ○ | ○ |
| Comparative example 7 | ○ | × | ○ |
From the result of table 2 it is clear that the etching agent composite of embodiment 1 to 4, uses and be based on the etchant combination
The total weight of object be 0.01 to 3wt% amount nitrate compound, observe lateral erosion less than 0.2 μm, both there is no residue or
There is no the erosions to lower layer.
However, generating excessive lateral erosion, and see in the etching agent composite of the comparative example 1 without nitrate compound
Residue and the erosion to lower layer are observed, and observes the erosion to lower layer in the etching agent composite of comparative example 2.
In addition, respectively including potassium sulfate and ammonium acetate instead of the etchant of the comparative example 3 and 4 of the nitrate compound
In composition, residue is not generated, it has been observed that excessive lateral erosion and the erosion to lower layer.
In the etchant combination that the amount using nitric acid is more than the comparative example 5 of 12wt% based on the total weight of etching agent composite
In object and using chlorine compound amount be more than 5wt% the etching agent composite of comparative example 6 in, be both not observed residue or
Not to the erosion of lower layer, but generate excessive lateral erosion.
In addition, in the amount using nitrate compound being more than the ratio of 3wt% based on the total weight of the etching agent composite
It in etching agent composite compared with example 7, limits lateral erosion and does not corrode lower layer, but generate residue.
Therefore, including the total weight based on etching agent composite be 0.01 to 3wt% amount nitrate compound basis
Etching agent composite of the invention has the ability for etching thick indium oxide layer, and can etch the indium oxide layer without
Damage is arranged in the lower layer under the indium oxide layer.
Although illustratively disclosing the preferred embodiment of the present invention, those skilled in the art will
Understand, under without departing substantially from scope and spirit of the present invention as disclosed in the accompanying claims, various modifications, addition and substitution
It is possible.
Claims (4)
1. for etching the etching agent composite of indium oxide layer comprising: the total weight based on the etching agent composite, 5 to
The nitric acid or nitrous acid of 12wt%, 0.01 to 5wt% chlorine compound, 0.01 to 3wt% nitrate compound and surplus
Water, so that the total weight of the etching agent composite is 100wt%,
Wherein the chlorine compound includes being selected from least one of group as composed by sodium chloride, potassium chloride and ammonium chloride,
Wherein the nitrate compound includes at least one in the group as composed by sodium nitrate, ammonium nitrate and potassium nitrate
Kind.
2. etching agent composite according to claim 1, wherein the indium oxide layer includes selected from by indium tin oxide layer, oxygen
Change at least one of indium zinc layers, group composed by tin indium oxide zinc layers and indium gallium zinc layers.
3. etching agent composite according to claim 1, wherein the indium oxide layer have 500 toThickness.
4. etching agent composite according to claim 1 further includes selected from the group as composed by screening agent and corrosion inhibitor
At least one of.
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| CN201610079267.3A CN105907396A (en) | 2015-02-23 | 2016-02-04 | Etching solution composition for indium oxide layer and manufacturing method of an array substrate for liquid crystal display using the same |
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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 |
| KR20100027513A (en) * | 2008-09-02 | 2010-03-11 | 동우 화인켐 주식회사 | Manufacturing method of array substrate for liquid crystal display |
| 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 |
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| GB499627A (en) * | 1937-04-08 | 1939-01-26 | Aluminium Walzwerke Singen | Improvements in and relating to methods of making electrodes for electrolytic condensers |
| 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 |
| 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 |
| KR101953215B1 (en) * | 2012-10-05 | 2019-03-04 | 삼성디스플레이 주식회사 | Etchant composition, metal wiring and method of manufacturing a display substrate |
| KR20140086669A (en) * | 2012-12-28 | 2014-07-08 | 동우 화인켐 주식회사 | Etchant composition for metal oxide layer |
| KR20140086666A (en) * | 2012-12-28 | 2014-07-08 | 동우 화인켐 주식회사 | Etchant composition for metal oxide layer |
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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 |
| KR20100027513A (en) * | 2008-09-02 | 2010-03-11 | 동우 화인켐 주식회사 | Manufacturing method of array substrate for liquid crystal display |
| 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 |
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