CN105970223A - Etchant composition and manufacturing method of array substrate for liquid crystal display - Google Patents
Etchant composition and manufacturing method of array substrate for liquid crystal display Download PDFInfo
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- CN105970223A CN105970223A CN201610121213.9A CN201610121213A CN105970223A CN 105970223 A CN105970223 A CN 105970223A CN 201610121213 A CN201610121213 A CN 201610121213A CN 105970223 A CN105970223 A CN 105970223A
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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
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
Abstract
Disclosed are an etchant composition and a manufacturing method of an array substrate for a liquid crystal display. The etchant composition contains precious metal chemical complex, so shows a catalysis effect. Therefore, an amorphous silicon layer which is etched by a dry method or an amorphous silicon layer containing dopants can be further etched together with a metal wire by using a wet process etching technology.
Description
Technical field
The present invention relates to etching agent composite and make the side of the array base palte for liquid crystal display
Method.
Background technology
In semiconductor devices, on substrate, formation metal wire generally includes use sputtering method and forms gold
Belong to floor, coating photoresist, be exposed and develop so that photoresist is formed at selected district
Territory and being etched, was carried out technique before or after each single technique above-mentioned.
Photoresist is used to be etched technique as mask so that metal level is stayed on selection area, and
And etch process can include the dry etching using plasma etc. or use the wet method erosion of etching solution
Carve.
The nearest subject matter of this semiconductor equipment is the resistance of metal wire.This is because, just
For Thin Film Transistor-LCD (TFT-LCD), increasing panel size and realizing height
Resolution aspect, it is now recognized that it is critically important to solve RC signal delay problem, and this RC signal
Postpone mainly to be caused by resistance.Therefore, in order to reduce RC signal delay, (it is for increasing TFT-LCD
The important requirement of size), it is necessary to exploitation has low-resistance material.Although chromium accustomed to using
(Cr, resistivity: 12.7 × 10-8Ω m), molybdenum (Mo, resistivity: 5 × 10-8Ω m), aluminum (Al,
Resistivity: 2.65 × 10-8Ω m) and alloy, but they are difficult to apply to large size TFT-LCD
Gate line and data wire.
Therefore, there is low-resistance novel metal layer, such as, such as layers of copper and copper molybdenum layer etc
Copper base metal layer, and receive publicity for the etching agent composite of this novel metal layer and go deep into
Research.In consideration of it, Korean Patent Application Publication No.2010-0090538 discloses for etching
The etchant that copper/molybdenum alloy is double-deck, it includes hydrogen peroxide, organic acid, phosphate cpd, water
Dissolubility cyclic amine compound, molecule have nitrogen-atoms and the water soluble compound of carboxyl, contains fluorination
Compound, polyalchohols surfactants and water.But, this etchant is problematic, because
It cannot be used for etching method for amorphous silicon layer or the amorphous silicon layer containing alloy.
[reference listing]
[patent documentation]
Korean Patent Application Publication No.2010-0090538
Summary of the invention
Therefore, for the problem run in correlation technique, it is made that the present invention, and the present invention
Purpose be to provide etching agent composite, it makes generally by the amorphous silicon layer of dry etching or containing mixing
The amorphous silicon layer of foreign material can be used together wet etching process together with upper metal wire and be lost by a step
Carve.
The present invention is provided to the etching agent composite of etch copper base metal layer and silicon base layer, its bag
Include: the hydrogen peroxide of 10-35wt%, the organic acid of 0.5-5wt%, the phosphoric acid of 0.1-5wt% or phosphorus
Hydrochlorate, the water solublity cyclic amine compound of 0.1-5wt%, the molecule of 0.1-5wt% has amino and carboxylic
The water soluble compound of base, the fluorine compounds of 0.01-0.9wt%, the noble metal chemical combination of 0.01-2wt%
Thing, and the water of surplus.
In the exemplary embodiment, organic acid can include selected from acetic acid, butanoic acid, citric acid,
At least one in the group of formic acid, gluconic acid, glycolic, malonic acid and valeric acid composition.
In another illustrative embodiments, water solublity cyclic amine compound can include amino four
Azoles, imidazoles, indole, purine, pyrazoles, pyridine, pyrimidine, pyrroles, pyrrolidine, quinolinones and
At least one in the group of pyrrolin composition.
In another exemplary embodiment, molecule has the water soluble compound of amino and carboxyl
Can include selected from alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, ammonia
At least one in the group of triacetic acid and sarcosine composition.
In another illustrative embodiments, fluorine compounds can include selected from ammonium fluoride, sodium fluoride,
At least one in the group of potassium fluoride, ammonium acid fluoride, sodium bifluoride and potassium hydrogen fluoride composition.
In an also illustrative embodiments, precious metal chemical complex can include selected from copper, silver-colored and golden
At least one in the group of composition.
In another exemplary embodiment, copper base metal layer can be copper or the monolayer of copper alloy,
Or include molybdenum layer and on molybdenum layer formed layers of copper copper molybdenum layer, include Mo alloy and molybdenum close
The copper molybdenum alloy layer of the layers of copper formed in layer gold, include titanium layer and the copper of layers of copper formed on titanium layer
Titanium layer or include titanium alloy layer and the copper-titanium alloy layer of layers of copper formed on titanium alloy layer.
Additionally, the invention provides the method making the array base palte for liquid crystal display, its
Including: a) on substrate, form gate line；B) on the substrate include gate line, grid is formed
Insulating barrier；C) on gate insulator, semiconductor layer is formed；D) source is formed on the semiconductor layer
Electrode and drain electrode；With e) formation is connected to the pixel electrode of drain electrode, a) is included in
Form copper base metal layer on substrate and use etching agent composite etch copper base metal layer, thus shape
Become gate line, d) include forming copper base metal layer and using etching agent composite etch copper fund
Belong to layer, thus form source electrode and drain electrode, and etching agent composite includes, based on described group
The gross weight of compound, the hydrogen peroxide of 10-35wt%, the organic acid of 0.5-5wt%, 0.1-5wt%
Phosphoric acid or phosphate, the water solublity cyclic amine compound of 0.1-5wt%, in the molecule of 0.1-5wt%
There is the water soluble compound of amino and carboxyl, the fluorine compounds of 0.01-0.9wt%, 0.01-2wt
The precious metal chemical complex of %, and the water of surplus.
In the exemplary embodiment, array base palte can be thin film transistor (TFT) (TFT) array base
Plate.
In another exemplary embodiment, copper base metal layer can be copper or the monolayer of copper alloy,
Or include molybdenum layer and on molybdenum layer formed layers of copper copper molybdenum layer, include Mo alloy and molybdenum close
The copper molybdenum alloy layer of the layers of copper formed in layer gold, include titanium layer and the copper of layers of copper formed on titanium layer
Titanium layer or include titanium alloy layer and the copper-titanium alloy layer of layers of copper formed on titanium alloy layer.
According to the present invention, etching agent composite comprises precious metal chemical complex therefore to show catalysis effect
Really, the most generally by the amorphous silicon layer of dry etching or containing the amorphous silicon layer of alloy, it is possible to use
Wet etching process together with upper metal wire by a step etching.
Detailed description of the invention
The present invention relates to etching agent composite and the making side of the array base palte for liquid crystal display
Method.Etching agent composite according to the present invention includes precious metal chemical complex, therefore shows catalysis effect
Really, thus, the amorphous silicon layer of dry etching or the amorphous silicon layer containing alloy is generally used to pass through
Wet etching together with upper metal wire by a step etching.
Hereinafter, the present invention will be provided detailed description.
Present invention discusses the etching agent composite for etch copper base metal layer and silicon base layer, its bag
Include: the hydrogen peroxide of 10-35wt%, the organic acid of 0.5-5wt%, the phosphoric acid of 0.1-5wt% or phosphoric acid
Salt, the water solublity cyclic amine compound of 0.1-5wt%, the molecule of 0.1-5wt% has amino and carboxyl
Water soluble compound, the fluorine compounds of 0.01-0.9wt%, the precious metal chemical complex of 0.01-2wt%,
Water with surplus.
By means of the etching agent composite according to the present invention, film crystal in LCD or OLED
Copper/Mo alloy in the line (line, i.e. circuit) of pipe or copper/titanium alloy layer are for use as the line of circuit
Form provide.The silicon-based active layer generally formed by dry etching can use above-mentioned etchant
It is easily wet etched with the catalysis activity of noble metal, therefore reduces process costs and time.
Copper base metal layer can be copper or the monolayer of copper alloy or include molybdenum layer and on molybdenum layer shape
Become layers of copper copper molybdenum layer, include Mo alloy and on Mo alloy formed layers of copper copper molybdenum close
Layer gold, include titanium layer and on titanium layer formed layers of copper copper titanium layer or include titanium alloy layer and
The copper-titanium alloy layer of the layers of copper formed on titanium alloy layer.
Especially, Mo alloy can include molybdenum monolayer or molybdenum and selected from titanium (Ti), tantalum (Ta),
In chromium (Gr), nickel (Ni), neodymium (Nd), aluminum (Al), palladium (Pd) and indium (In)
At least one, and titanium alloy layer can include titanium monolayer or titanium and selected from molybdenum (Mo), tantalum (Ta),
In chromium (Gr), nickel (Ni), neodymium (Nd), aluminum (Al), palladium (Pd) and indium (In)
At least one.
Silicon base layer can include silicon or the non-crystalline silicon containing alloy.In the non-crystalline silicon containing alloy,
Alloy can include boron (B) or phosphorus (P).
Copper/Mo alloy or copper/titanium alloy layer are to be placed in Mo alloy or titanium alloy layer above layers of copper
Or the double-deck form of lower section provides, or so that Mo alloy or titanium alloy layer are placed in layers of copper
The form of the three-decker of side and lower section provides.
Substrate is for TFT-LCD, TFT-OLED and the base of touch sensor panel (TSP)
Plate is exemplified.
Etching agent composite according to the present invention makes gate line and the use in display device for gate electrode
In data electrode data wire can a step etching, wherein gate line and data wire include layers of copper and molybdenum
Alloy-layer or layers of copper and titanium alloy layer.
In etching agent composite, with the amount bag of 10-35wt% based on etching agent composite gross weight
Containing hydrogen peroxide.On the one hand, if the amount of hydrogen peroxide is less than 10wt%, etch-rate substantially becomes
Slowly, therefore make this technique be difficult to carry out, and can not fully etch, adversely produce etching
Residue, copper therein, Mo alloy, titanium alloy layer and silicon base layer can not be etched effective and
Its part may be left over.On the other hand, if the amount of hydrogen peroxide is more than 35wt%, it is difficult to control
Etch-rate, also has, in etching process procedure, due to the freedom with the metal of such as copper etc
Base reacts and may individually accelerate the reaction of hydrogen peroxide, and has the danger of blast.
In etching agent composite, with the amount bag of 0.5-5wt% based on etching agent composite gross weight
Containing organic acid.Organic acid is mainly used in etched copper and Mo alloy or copper together with hydrogen peroxide
Layer and titanium layer.Organic acid has the purity being applicable to semiconductor technology and hydrogen peroxide, and preferably wraps
Containing ppb level or less metal impurities.Organic acid plays the effect of regulation pH to control the speed of etch copper
Rate and etching molybdenum alloy or the speed of titanium alloy.When with the addition of organic acid, pH be appropriately positioned into
The scope of about 0.5-4.5.
Organic acid can include selected from acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, ethanol
Any one in acid, malonic acid and valeric acid.
In etching agent composite, with the amount bag of 0.5-5wt% based on etching agent composite gross weight
Phosphoric acid or phosphate.(it is vertical for obtaining the good tapered profiles of line for phosphoric acid or phosphate
In the angle that lower floor is formed), and electrical effect (the former electricity between molybdenum alloy or titanium alloy and copper can be reduced
Pond effect, galvanic effect), thus prevent undercut, wherein Mo alloy or titanium alloy
Layer is etched away from below layers of copper.On the one hand, if not using phosphoric acid or phosphate, or to be less than
The amount of 0.1wt% comprises phosphoric acid or phosphate, then away from over etching molybdenum alloy possible below upper layers of copper
Layer or titanium alloy layer.Under serious conditions, pattern may be peeled off from substrate.On the other hand, if phosphorus
Sour or phosphatic amount reduces Mo alloy or the etch-rate of titanium alloy layer more than 5wt%, possibility,
And due to conditions of streaking it may happen that electrical short.
Various types of phosphate can be used, and phosphate is preferably selected from: wherein one of phosphoric acid,
The salt that two or three hydrogen atoms are replaced by alkali metal or alkaline-earth metal.Phosphatic example can be wrapped
Include sodium dihydrogen phosphate and potassium dihydrogen phosphate etc..
In etching agent composite, with the amount bag of 0.1-5wt% based on etching agent composite gross weight
Containing water-soluble cyclic amine compound.Water solublity cyclic amine compound rise regulation copper molybdenum alloy etch-rate and
Reduce the effect of CD loss (loss of bar width) of pattern, thus increase process margin.On the one hand,
If not using water solublity cyclic amine compound or comprising water solublity cyclammonium chemical combination with the amount less than 0.1wt%
During thing, it is difficult to control etch-rate, and desirable pattern width can not be obtained, adversely increase defect
Rate and owing to low process margin causes problem when large-scale production.On the other hand, if water-soluble
The amount of property cyclic amine compound may substantially reduce more than 5wt%, etch-rate, the etching therefore obtained
Agent may not apply to this technique.
Various types of water solublity cyclic amine compound can be used.Be preferably used selected from Aminotetrazole,
Imidazoles, indole, purine, pyrazoles, pyridine, pyrimidine, pyrroles, pyrrolidine, quinolinones and pyrroles
Any one in quinoline.
In etching agent composite, with the amount bag of 0.1-5wt% based on etching agent composite gross weight
Containing the water soluble compound in molecule with amino and carboxyl.Described molecule has amino and carboxyl
Water soluble compound in etchant storage process, act the effect preventing hydrogen peroxide selfdecomposition.Enter one
Step ground, in the case of etching mass substrate, prevents etching performance with the amount being etched metal ion
Increase and change.When there is in containing molecule the water soluble compound of amino and carboxyl, dioxygen
The decomposition rate of water is down to about 1/10, has thereby ensure that have storage persistent period and stability
Profit impact.Additionally, substantially when etch copper, Mo alloy and titanium alloy layer produced copper from
Son, molybdenum alloy ion and titanium alloy ion are inactivated by chelatropic reaction, therefore prevent due to these
Ion and there is other reaction.Therefore, even if when etching substantial amounts of substrate, etching performance is not
Change with the increase of concentration of metal ions.Especially for layers of copper, a lot of when existing in etchant
During copper ion, the oxidized blackening of passivation layer and situation about not being further etched may often occur,
But, this can be prevented in the case of there is above-claimed cpd.If molecule has amino
With the amount of the water soluble compound of carboxyl more than 5wt%, etch-rate may be adversely affected,
Thus etching agent composite hinders and forms metal wire with desired form, adversely causes defect.
Molecule has the water soluble compound of amino and carboxyl can be selected from alanine, aminobutyric acid,
Glutamic acid, glycine, iminodiacetic acid, nitrilotriacetic acid and sarcosine.
In etching agent composite, with the amount of 0.1-0.9wt% based on etching agent composite gross weight
Comprise fluorine compounds.Fluorine compounds act the effect removing residue, this residue substantially by with
Solution in etched copper and Mo alloy produces, and dissociating to realization by fluorion
Surface is played an important role by the etching of the silicon layer of hydrogen peroxide oxidation.Further, fluorine compounds pass through
Dissociate and be used as by the primary etchant of the silicon-based active layer of hydrogen peroxide oxidation.
It is known that, conventionally, copper is etched effective under low pH (2-4), and molybdenum alloy in faintly acid or
It is etched effective under neutral pH (5-7).In order to while etched copper and Mo alloy, have
Necessity is etched for any one concentration in layers of copper and Mo alloy.Like this, focus on relatively
On thick-layer.Due to layers of copper thickness much, pH is relatively low.The etchant of the pH with about 2-4 can
With fairly slow etch-rate etching Mo alloy, the most effectively etched copper.But, due to molybdenum
The character of alloy-layer, it is possible to create the residue of small particles form.Therefore, when the residue produced
When remaining on glass substrate up or down layer, it is possible to create short circuit, or reduce luminosity.In order to go
Except residue, it is necessary to fluorine compounds are added in etchant.Glass substrate, silicon nitride and oxidation
Silicon layer may adversely be fluorinated compound and be etched, but it is etched in and comprises fluorine with low-down concentration
Can be avoided under conditions of compound.
According in the etching agent composite of the present invention, with the addition of fluorination with the amount of 0.01-0.9wt% and close
Thing.The scope of given above-mentioned amount, the silicon-based active layer including porous silicon or the silicon containing alloy is eclipsed
Carve, and glass substrate, silicon nitride and the silicon oxide layer as passivation layer is not etched by.Even if when adding
When adding fluorine compounds the most in a small amount, it is also possible to fully remove the residue of Mo alloy.
Various types of fluorine compounds can be used, and fluorine compounds can be selected from ammonium fluoride, fluorine
Change sodium, potassium fluoride, ammonium acid fluoride, sodium bifluoride and potassium hydrogen fluoride.
In etchant, comprising noble metal with the amount of 0.1-2wt%, noble metal is used as to reduce activation energy
Catalyst with promote silicon face by hydrogen peroxide oxidation.Its surface is by precious metal chemical complex and peroxide
The silicon layer changing hydroxide is fluorinated compound oxidation.
On the one hand, if the amount of precious metal chemical complex is less than 0.1wt%, it can not play metallic catalyst
Effect so that silicon-based active layer can not be etched.On the other hand, if precious metal chemical complex
Measure more than 2wt%, owing to its character adds the radical reaction promoted with metal, therefore peroxide may be increased
Change the decomposition of hydrogen.Accordingly, because the concentration of hydrogen peroxide reduces, etch-rate is likely to reduce,
Adversely lose the inherent function of etchant.In the case of fierceness is decomposed, it may occur however that blast.
Precious metal chemical complex can include at least one in the group of copper, silver and gold composition, also
Copper compound and silver compound etc. can be included.
Copper compound preferably includes in copper nitrate, copper sulfate, cupric phosphate, copper chloride and copper acetate
Any one, and silver compound preferably includes any one in silver nitrate, silver sulfate and silver phosphate.
Water is not particularly limited, but preferably includes deionized water.It is especially useful that there is 18M Ω/cm
Or the deionized water of bigger resistivity (it is the degree removing deionization from water).
If it is necessary, typical additive can be added further.Its example is not particularly limited, but one
As include surfactant, chelating agen and corrosion inhibitor.
In order to increase etch uniformity, add surfactant to reduce surface tension, its kind without
Limit especially, as long as it can withstand etchant and provide with compatible form.Its example is permissible
Including anion surfactant, cationic surfactant, amphoteric surfactant and nonionic
Surfactant.Be preferably used is fluorine based surfactant.
Additionally, present invention discusses the method making the array base palte for liquid crystal display, its
Including: a) on substrate, form gate line；B) on the substrate include gate line, grid is formed
Insulating barrier；C) on gate insulator, semiconductor layer is formed；D) source is formed on the semiconductor layer
Electrode and drain electrode；With e) formation is connected to the pixel electrode of drain electrode, a) is included in
Form copper base metal layer on substrate and use etching agent composite etch copper base metal layer, thus shape
Become gate line, d) include forming copper base metal layer and using etching agent composite etch copper fund
Belong to layer, thus form source electrode and drain electrode, and etching agent composite includes, based on described group
The gross weight of compound, the hydrogen peroxide of 10-35wt%, the organic acid of 0.5-5wt%, 0.1-5wt%
Phosphoric acid or phosphate, the water solublity cyclic amine compound of 0.1-5wt%, in the molecule of 0.1-5wt%
There is the water soluble compound of amino and carboxyl, the fluorine compounds of 0.01-0.9wt%, 0.01-2wt
The precious metal chemical complex of %, and the water of surplus.
By following only detailed with explanation present invention embodiment, comparative example and test case as starting point
The present invention is described, but the invention is not restricted to described embodiment, comparative example and test case and can carry out
Various modifications and changes.
Embodiment 1-23 and the making of comparative example 1-14: etching agent composite
The component using the amount (wt%) shown in table 1 below and table 2 below prepares etching agent composite.
[table 1]
[table 2]
Test case 1: etching characteristic evaluation
By depositing copper (Cu) respectively on glass substrate (100mm × 100mm), molybdenum titanium closes
Layer gold (MoTi), titanium layer (Ti) and hydrogenated amorphous silicon layer (a-Si:H) are extremelyThickness
And make substrate.
Use the etching agent composite etching aforementioned four in embodiment 1-23 and comparative example 1-14 respectively
Sample.In the etch process, use spraying etching machine (ETCHER is manufactured) by SEMES,
And the temperature of etching agent composite is arranged to 30 DEG C.When temperature arrives 30 ± 0.1 DEG C, respectively
Individual sample is etched 20s (second), 40s, 60s, 80s and 100s.After cleaning and being dried, make
Etched thickness in time is measured by scanning electron microscope (S-4700 is manufactured by HITACHI),
And based on the evaluation criterion evaluation in table 3.Result such as table 4 below and table 5 below.
The evaluation of test case 2:pH
PH meter (Orion3star is manufactured by Thermoscientific) is used to measure embodiment 1-23
With the pH of each etching agent composite in comparative example 1-14, and based on the evaluation criterion evaluation in table 3.
Result such as table 4 below and table 5 below.
Test case 3: the evaluation of over etching
By successively by hydrogenated amorphous silicon layer (a-Si:H), the amorphous silicon hydride of Doping Phosphorus (P)
Layer (n+a-Si:H), molybdenum titanium alloy layer (MoTi) and copper (Cu) are deposited on glass substrate (100mm
× 100mm) above make substrate.As another sample, by successively by hydrogenated amorphous silicon layer
(a-Si:H), the hydrogenated amorphous silicon layer (n+a-Si:H) of Doping Phosphorus, titanium layer (Ti) and copper (Cu)
It is deposited on glass substrate (100mm × 100mm) and above makes substrate.Afterwards, produce each
The individual sample all with photoresist (PR), this photoresist has by being lithographically formed
Predetermined pattern.
Use each etching agent composite etching above-mentioned two in embodiment 1-23 and comparative example 1-14
Sample.In the etch process, use spraying etching machine (ETCHER is manufactured) by SEMES,
And the temperature of etching agent composite is arranged to 30 DEG C.When temperature arrives 30 ± 0.1 DEG C, respectively
Individual sample is etched 60s.After cleaning and being dried, use scanning electron microscope (S-4700, by
HITACHI manufactures) observe its cross section, and observe molybdenum alloy or titanium whether away from upper layers of copper below
And based on the evaluation criterion evaluation in table 3.Result such as table 4 below and table 5 below.
Test case 4: the evaluation of side etching
By successively by hydrogenated amorphous silicon layer (a-Si:H), Doping Phosphorus hydrogenated amorphous silicon layer (n+a-Si:
H), molybdenum titanium alloy layer (MoTi) and copper (Cu) are deposited on glass substrate (100mm × 100mm)
Above make substrate.As another sample, by successively by hydrogenated amorphous silicon layer (a-Si:H),
The hydrogenated amorphous silicon layer (n+a-Si:H) of Doping Phosphorus, titanium layer (Ti) and copper (Cu) are deposited on glass
Glass substrate (100mm × 100mm) is upper and makes substrate.Afterwards, produce and each have
The sample of photoresist (PR), this photoresist has the predetermined pattern by being lithographically formed.
Use each etching agent composite etching above-mentioned two in embodiment 1-23 and comparative example 1-14
Sample.In the etch process, use spraying etching machine (ETCHER is manufactured) by SEMES,
And the temperature of etching agent composite is arranged to 30 DEG C.When temperature arrives 30 ± 0.1 DEG C, respectively
Individual sample is etched 60s.After cleaning and being dried, use scanning electron microscope (S-4700, by
HITACHI manufactures) observe its side etching length, and based on the evaluation criterion evaluation in table 3.
Result such as table 4 below and table 5 below.
Test case 5: residue evaluation
By successively by hydrogenated amorphous silicon layer (a-Si:H), Doping Phosphorus hydrogenated amorphous silicon layer (n+a-Si:
H), molybdenum titanium alloy layer (MoTi) and copper (Cu) are deposited on glass substrate (100mm × 100mm)
Above make substrate.As another sample, by successively by hydrogenated amorphous silicon layer (a-Si:H),
The hydrogenated amorphous silicon layer (n+a-Si:H) of Doping Phosphorus, titanium layer (Ti) and copper (Cu) are deposited on glass
Glass substrate (100mm × 100mm) is upper and makes substrate.Afterwards, produce and each have
The sample of photoresist (PR), this photoresist has the predetermined pattern by being lithographically formed.
Use each etching agent composite etching above-mentioned two in embodiment 1-23 and comparative example 1-14
Sample.In the etch process, use spraying etching machine (ETCHER is manufactured) by SEMES,
And the temperature of etching agent composite is arranged to 30 DEG C.When temperature arrives 30 ± 0.1 DEG C, respectively
Individual sample is etched 60s.After cleaning and being dried, use scanning electron microscope (S-4700, by
HITACHI manufactures) observe its etching surface, and see whether layers of copper not to be possible to determine when the sample has been completely etched and have residual
Stay, and be evaluated based on the evaluation criterion in table 3.Result such as table 4 below and table 5 below.
Test case 6: blast is evaluated
When each etching agent composite in embodiment 1-23 and comparative example 1-14 is stored in thermostat
Time middle, measure the temperature of its 24h.See whether to produce the anti-of 30 DEG C or more heat or fierceness
Should, and be evaluated based on the evaluation criterion in table 3.Result such as table 4 below and table 5 below.
[table 3]
[table 4]
[table 5]
Although being in illustration purpose to disclose the preferred embodiment of the present invention, but, this area skill
Art personnel should be understood that without departing substantially from the scope and spirit of the present invention as disclosed in claims
In the case of, various amendments, to add and substitute be possible.
Claims (10)
1. for etch copper base metal layer and the etching agent composite of silicon base layer, comprising:
Gross weight based on described compositions,
The hydrogen peroxide of 10-35wt%,
The organic acid of 0.5-5wt%,
The phosphoric acid of 0.1-5wt% or phosphate,
The water solublity cyclic amine compound of 0.1-5wt%,
The molecule of 0.1-5wt% has the water soluble compound of amino and carboxyl,
The fluorine compounds of 0.01-0.9wt%,
The precious metal chemical complex of 0.01-2wt%, and
The water of surplus.
Etching agent composite the most according to claim 1, wherein said organic acid includes being selected from
Acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic, malonic acid and valeric acid composition
At least one in group.
Etching agent composite the most according to claim 1, wherein said water solublity cyclammonium chemical combination
Thing includes Aminotetrazole, imidazoles, indole, purine, pyrazoles, pyridine, pyrimidine, pyrroles, pyrroles
At least one in the group of alkane, quinolinones and pyrrolin composition.
Etching agent composite the most according to claim 1, has amino and carboxylic in its Middle molecule
The described water soluble compound of base include selected from alanine, aminobutyric acid, glutamic acid, glycine,
At least one in the group of iminodiacetic acid, nitrilotriacetic acid and sarcosine composition.
Etching agent composite the most according to claim 1, wherein said fluorine compounds include choosing
Group from ammonium fluoride, sodium fluoride, potassium fluoride, ammonium acid fluoride, sodium bifluoride and potassium hydrogen fluoride composition
In at least one.
Etching agent composite the most according to claim 1, wherein said precious metal chemical complex bag
Include at least one in the group of copper, silver and gold composition.
Etching agent composite the most according to claim 1, wherein said copper base metal layer is copper
Or the monolayer of copper alloy or include molybdenum layer and on molybdenum layer formed layers of copper copper molybdenum layer, include
Mo alloy and on Mo alloy formed layers of copper copper molybdenum alloy layer, include titanium layer and at titanium layer
The copper titanium layer of the layers of copper of upper formation or include titanium alloy layer and the layers of copper that formed on titanium alloy layer
Copper-titanium alloy layer.
8. the method making the array base palte for liquid crystal display, comprising:
A) on substrate, gate line is formed；
B) on the substrate including described gate line, gate insulator is formed；
C) on described gate insulator, semiconductor layer is formed；
D) on described semiconductor layer, source electrode and drain electrode are formed；With
E) formation is connected to the pixel electrode of described drain electrode,
A) it is included on substrate formation copper base metal layer and uses etching agent composite to etch
Described copper base metal layer, thus form described gate line,
D) include forming copper base metal layer and using etching agent composite to etch described copper base metal
Layer, thus form described source electrode and described drain electrode, and
Described etching agent composite includes, gross weight based on described compositions, the mistake of 10-35wt%
Hydrogen oxide, the organic acid of 0.5-5wt%, the phosphoric acid of 0.1-5wt% or phosphate, 0.1-5wt%
Water solublity cyclic amine compound, the molecule of 0.1-5wt% has the water solublity chemical combination of amino and carboxyl
Thing, the fluorine compounds of 0.01-0.9wt%, the precious metal chemical complex of 0.01-2wt%, and the water of surplus.
Method the most according to claim 8, wherein said array base palte is thin film transistor (TFT) battle array
Row substrate.
Method the most according to claim 8, wherein said copper base metal layer is copper or copper conjunction
Gold monolayer or include molybdenum layer and on molybdenum layer formed layers of copper copper molybdenum layer, include molybdenum alloy
Layer and on Mo alloy formed layers of copper copper molybdenum alloy layer, include titanium layer and on titanium layer formed
Layers of copper copper titanium layer or include titanium alloy layer and on titanium alloy layer formed layers of copper copper titanium close
Layer gold.
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| KR10-2015-0034253 | 2015-03-12 | ||
| KR1020150034253A KR102265890B1 (en) | 2015-03-12 | 2015-03-12 | Etchant composition and manufacturing method of an array for liquid crystal display |
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| Country | Link |
|---|---|
| KR (1) | KR102265890B1 (en) |
| CN (1) | CN105970223A (en) |
| TW (1) | TW201638393A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106601614A (en) * | 2016-12-30 | 2017-04-26 | 常州亿晶光电科技有限公司 | Method for etching aluminum film of amorphous silicon solar cell |
| CN108930037A (en) * | 2017-05-22 | 2018-12-04 | 东友精细化工有限公司 | Metal film etchant and the conductive pattern forming method for utilizing it |
| CN109112539A (en) * | 2017-06-23 | 2019-01-01 | 东友精细化工有限公司 | Etchant |
| CN110396693A (en) * | 2018-04-25 | 2019-11-01 | 达兴材料股份有限公司 | Etchant and engraving method and manufacture display device or method for semiconductor containing IGZO using it |
| CN114164003A (en) * | 2021-12-06 | 2022-03-11 | Tcl华星光电技术有限公司 | Etchant composition for display panel and etching method of display panel |
| CN116120936A (en) * | 2022-10-27 | 2023-05-16 | 上海天承化学有限公司 | Etching liquid medicine and preparation method and application thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102070323B1 (en) * | 2016-10-14 | 2020-01-29 | 주식회사 이엔에프테크놀로지 | Etching Composition |
| KR102543520B1 (en) * | 2021-03-10 | 2023-06-15 | 소니드 주식회사 | Etching composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080024818A (en) * | 2006-09-15 | 2008-03-19 | 동우 화인켐 주식회사 | Composition of etching solutions for multilayers of cu and molybdenum |
| KR101529733B1 (en) | 2009-02-06 | 2015-06-19 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
| KR20110115814A (en) * | 2010-04-16 | 2011-10-24 | 주식회사 동진쎄미켐 | Etchant and method for preparing electronic device |
| KR20130068116A (en) * | 2011-12-15 | 2013-06-25 | 동우 화인켐 주식회사 | Etching solution for array substrate and method of manufacturing array substrate using the same |
| KR102028578B1 (en) * | 2012-12-24 | 2019-10-04 | 동우 화인켐 주식회사 | Method of preparing array of thin film transistor |
| KR20140084417A (en) * | 2012-12-26 | 2014-07-07 | 동우 화인켐 주식회사 | Echaing composition for preparing a channel of thin film transistor and method of preparing a channel of thin film transistor |
-
2015
- 2015-03-12 KR KR1020150034253A patent/KR102265890B1/en active IP Right Grant
-
2016
- 2016-02-26 TW TW105105912A patent/TW201638393A/en unknown
- 2016-03-03 CN CN201610121213.9A patent/CN105970223A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106601614A (en) * | 2016-12-30 | 2017-04-26 | 常州亿晶光电科技有限公司 | Method for etching aluminum film of amorphous silicon solar cell |
| CN108930037A (en) * | 2017-05-22 | 2018-12-04 | 东友精细化工有限公司 | Metal film etchant and the conductive pattern forming method for utilizing it |
| CN109112539A (en) * | 2017-06-23 | 2019-01-01 | 东友精细化工有限公司 | Etchant |
| CN110396693A (en) * | 2018-04-25 | 2019-11-01 | 达兴材料股份有限公司 | Etchant and engraving method and manufacture display device or method for semiconductor containing IGZO using it |
| CN110396693B (en) * | 2018-04-25 | 2021-08-10 | 达兴材料股份有限公司 | Etching liquid composition, etching method using same, and method for producing display device or semiconductor containing IGZO |
| CN114164003A (en) * | 2021-12-06 | 2022-03-11 | Tcl华星光电技术有限公司 | Etchant composition for display panel and etching method of display panel |
| CN116120936A (en) * | 2022-10-27 | 2023-05-16 | 上海天承化学有限公司 | Etching liquid medicine and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102265890B1 (en) | 2021-06-16 |
| KR20160109569A (en) | 2016-09-21 |
| TW201638393A (en) | 2016-11-01 |
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