CN107447215A - The method of array substrate for liquid crystal display device is manufactured for the etchant of copper base metal film and using it - Google Patents
The method of array substrate for liquid crystal display device is manufactured for the etchant of copper base metal film and using it Download PDFInfo
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- CN107447215A CN107447215A CN201710205825.0A CN201710205825A CN107447215A CN 107447215 A CN107447215 A CN 107447215A CN 201710205825 A CN201710205825 A CN 201710205825A CN 107447215 A CN107447215 A CN 107447215A
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- 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
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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
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- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
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- C23F1/18—Acidic compositions for etching copper or alloys thereof
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- 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
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- 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
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- 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
- G02F1/1343—Electrodes
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- 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
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
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- 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
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
- G02F1/136295—Materials; Compositions; Manufacture processes
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Abstract
The present invention relates to the method that the etchant for copper base metal film and manufacture include its array substrate for liquid crystal display device, in more detail, it is related to the method for including its array substrate for liquid crystal display device comprising the lewis acidic etchant for copper base metal film and manufacture, this is used for copper base metal film etchant and passed through comprising lewis acid, the etching rejection of the cyclic amine compound in the etchant for copper base metal film can be reduced, so that the etching inhibitor performance change occurred with the progress of etching reaction minimizes.
Description
Technical field
Liquid crystal display device array is manufactured the present invention relates to the etchant for copper base metal film and using it
The method of substrate, its minimum that etching characteristic of etchant can be changed with time.
Background technology
The process for forming metal wire on substrate in semiconductor devices generally forms work by the metal film by sputtering etc.
Skill, photoresist coat, technique and etch process of photoresist etc. are formed in institute constituency by exposed and developed
Step forms, and is included in washing process before and after discrete units technique etc..The etch process is referred to by by photoresist
Agent forms the technique of metal film as mask and in institute constituency, usually using the dry etching using plasma etc. or utilizes erosion
Carve the wet etching of liquid composition.
In this semiconductor device, the resistance of metal wire recently becomes the problem of being primarily upon.Because resistance is
The principal element of RC signal delays is caused, especially, in TFT-LCD display device (thin film
Transistor-liquid crystal display, TFT-LCD) in the case of, the increase of panel size and realize high-resolution
Rate is the key of technological development, and therefore, TFT-LCD maximization necessarily requires to reduce RC signal delays, to achieve it,
Low-resistance material must be developed.Accordingly, it is difficult to by the chromium mainly used (Cr, ratio resistance in the past：12.7×10-8Ω m), molybdenum
(Mo, ratio resistance：5×10-8Ω m), aluminium (Al, ratio resistance：2.65×10-8Ω m) and its alloy be used as in large-scale TFT-LCD
Grid and data wire for using etc..
Under above-mentioned background, as new low resistive metal film, the copper base metal such as copper film and copper-molybdenum film film and its etching solution
Composition is paid high attention to.Although however, currently used various types of etchants for copper film metal film,
It is that can not meet the performance required by user.Especially, as handled copper base metal film quantity increases, combined in etching solution
Cu in thing2+Also increase together, the problem of reduction so as to which the disposal ability of etchant occur over time,
Therefore there is an urgent need to studied to solve the above problems.
In order to solve the above problems, Korean Patent Publication No. 2016-0002312 is disclosed by using Cu2+Stabilization
Agent (that is, chelating agent), to suppress with handled copper base metal film quantity and the Cu in increased etchant2+Work
Scheme.However, there are the following problems：The etching energy of etchant can not be fully prevented using only above-mentioned chelating agent
Power reduces over time.
[prior art literature]
[patent document]
Korean Patent Publication No. 2016-0002312 (on January 7th, 2016, Soulbrain companies)
The content of the invention
Technical problem
In order to solve the above problems, it is an object of the invention to provide a kind of etching solution combination for copper base metal film
Thing, it is enabled to etching reaction by reducing the etching rejection of the cyclic amine compound at etching reaction initial stage
Progress and the etching solution performance change that occurs minimizes.
Etchant manufacture liquid crystal display device array base is utilized it is further an object that providing
The method of plate.
Technical scheme
In order to realize to above-mentioned purpose, it is characterised by including lewis acid according to the etchant of the present invention.
Beneficial effect
Had the effect that according to the etchant of the present invention：By the ring-type amine compounds for reducing etching reaction initial stage
The etching rejection of thing, and the etching solution performance change for enabling to occur with the progress of etching reaction minimizes.
In addition, the effect above is also had according to the array substrate for liquid crystal display device of the present invention.
Embodiment
In the present invention, when describing some parts of certain a part of " comprising ", this is not excluded for especially on the contrary
The other components of record, but other components can also be included.
Hereinafter, the preferred embodiment of the present invention is described in detail.
Copper base metal film
In the present invention, copper base metal film refers to including copper in the constituent of film, its concept include monofilm and
The multilayer film of such as duplicature.E.g., including monofilm of copper or copper alloy, copper-molybdenum film, copper-molybdenum alloy as multilayer film
Film and copper-metal oxide film etc..The copper-molybdenum film refers to the layers of copper for including molybdenum layer and being formed on the molybdenum layer, described
Copper-molybdenum alloy film refers to the layers of copper for including Mo alloy and being formed on the Mo alloy.In addition, the Mo alloy refers to
Be in the group that selection is made up of tin (Sn), titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), indium (In) etc. one
It is more than person with the alloy of molybdenum.Copper-the metal oxide film refers to including metal oxide layer and in the metal oxide
The layers of copper formed on layer.The metal oxide layer is the layer of the oxide containing metal, not special to the oxide of metal
Limitation.For example, the oxide of the metal can be selected from by zinc (Zn), tin (Sn), cadmium (Cd), gallium (Ga), aluminium (Al), beryllium
(Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), thallium (Tl), scandium (Sc), indium (In), yttrium (Y), lanthanum (La), actinium
(Ac), (Ta) are He the oxide of at least one of group that Furnace (Rf) is formed metal for titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum.
<Etchant>
Etchant according to an embodiment of the present invention includes lewis acid, in addition to this it is possible to including
More than one of metal film oxidant, etching accelerator, chelating agent, cyclic amine compound and fluorochemical, by the present invention
The etchant that is formed of structure have the effect that：Prevent by being increased according to handled copper base metal film quantity
Copper2+Caused etching solution efficiency reduces, so as to minimize the performance change of etching solution.
Lewis acid
Etchant according to an embodiment of the present invention includes lewis acid.
Had the effect that including the lewis acidic etchant：By the ring-type for reducing etching reaction initial stage
The etching rejection of amines, and can make to occur with the progress of etching reaction, by according to handled copper-based
Metal film quantity and increased copper2+Caused etching inhibitor performance change minimizes.
The lewis acid is that lewis acid used in this area limits without special, preferably includes to be selected from by Li+、
Na+、K+、Be+、Mg2+、Ca2+、Sr2+、Mn2+、Al3+、Sc3+、Ga3+、In3+、La3+、Gd3+、Lu3+、Cr3+、Co2+、Co3+、Fe2+、
Fe3+、Ti4+、Zr2+、Zr4+、Th4+、U4+、Pu4+、Ce3+、Hf4+、Ni2+、Cu+、Cu2+、Zn2+、Pb2+、Sn2+、Sn4+、Sb3+、Ir3+、
Bi3+、Rh3+、Ru2+、Os2+、Ag+、Au+、Tl+、Tl3+、Cd2+、Pb2+、Pt4+、UO2+、VO2+、WO4+、MnO3+、(CH3)2Sn2+、Be
(CH3)2、Al(CH3)3、AlCl3、AlH3、GaH3、Tl(CH3)3、Ga(CH3)3、GaCl3、GaI3、InCl3And RTe+The group formed
One of more than metal cation, in order to reduce cost, be more preferably selected from by Zn2+、Al3+、Fe3+、Sn4+And Zr2+Institute's structure
Into group in.
In addition, the lewis acid can be selected from by such as boron trifluoride, alchlor, titanium trichloride, titanium tetrachloride, chlorine
Change the metal halide of ferrous iron, iron chloride, zinc chloride, zinc bromide, stannous chloride, stannic chloride, stannous bromide, stannic bromide etc.；Three
Boron alkyl, trialkylaluminium, dialkylaluminum halides, monoalkyl aluminum halide, tetraalkyl tin, aluminium acetylacetonate, ferric acetyl acetonade, acetyl
Acetone zirconium, Dibutyltin oxide, dibutyltin acetoacetonate, dibutyl tin laurate, dioctyl tin maleate, aphthenic acids
It is magnesium, calcium naphthenate, manganese naphthenate, iron naphthenate, cobalt naphthenate, copper naphthenate, zinc naphthenate, zirconium naphthenate, lead naphthenate, pungent
Sour calcium, manganese octoate, iron octoate, cobalt octoate, zinc octoate, zirconium caprylate, tin octoate, lead octoate, zinc laurate, magnesium stearate, tristearin
In the group that sour aluminium, calcium stearate, cobaltous octadecanate, zinc stearate, lead stearate, aluminium acetate and zinc acetate etc. are formed.
The lewis acid can be the form with the compound of 5- methyl tetrazoliums.Lewis acid and 5- the methyl tetrazolium
Compound for example can be 5- methyl tetrazoliums zinc compound (Zn (MTZ)2, MTZ:5- methyl tetrazolium), 5- methyl tetrazoliums
Tin compound (Sn (MTZ)4), the aluminium compound (Al (MTZ) of 5- methyl tetrazoliums3), the iron compound (Fe of 5- methyl tetrazoliums
(MTZ)3), the titanium compound (Ti (MTZ) of 5- methyl tetrazoliums4), the zirconium compounds (Zr (MTZ) of 5- methyl tetrazoliums2) etc..These are changed
Both lewis acids and cyclic amine compound in the constituent that compound has the function that etchant can be performed
Advantage.
Relative to total 100 weight % etchant, the lewis acidic content can be 0.1 weight % to 5
Weight %, it is preferably 0.3 weight % to 3 weight %, more preferably 0.5 weight % to 2 weight %.In the lewis acid
During less than the scope, handled copper base metal film quantity increase effect is reduced, exceedes the scope in the lewis acid
When, the problem of etching characteristic that the etching solution at etching reaction initial stage be present can not be showed correctly.
Metal film oxidant
The etchant of the present invention can also include metal film oxidant.
The metal film oxidant is the main component for aoxidizing metal film, is not particularly limited, can be typically
One in the group being made up of hydrogen peroxide, peracetic acid, oxidized metal, nitric acid, persulfate, halogen acids, halate etc.
More than person, preferably can be hydrogen peroxide or persulfate.
The oxidized metal refers to oxidized metal.For example, refer to Fe3+、Cu2+Deng the oxidized metal is also wrapped
Include and be dissociated into Fe under solution state3+、Cu2+Deng compound.The persulfate includes ammonium persulfate, alkali metal persulfuric acid
Salt, potassium hydrogen persulfate etc., the halate include chlorate, perchlorate, bromate, Hyperbromic acid salt.
The metal film oxidant is the main component for aoxidizing copper.Relative to total 100 weight % etchant,
The content of the metal film oxidant is 1 weight % to 35 weight %, is preferably 5 weight % to 25 weight %, more preferably
For 10 weight % to 20 weight %.If meeting above range, preventing the rate of etch of copper reduces, and can realize appropriate amount
Etching, and excellent etching outline can be obtained.If however, being unsatisfactory for the scope, etch target film may be eclipsed
Carve, or overetch occurs, so as to cause pattern to lose and lose the function as metal wire.
The content of the metal film oxidant can be suitably regulated according to the species and characteristic of oxidant.
Etch accelerator
The etchant of the present invention can also include etching accelerator.
The etching accelerator is the cooxidant of the etching for copper film, and etching accelerator is according in etching solution
Content can control etching speed.In addition, the etching accelerator can be reacted with the copper ion in etchant,
Therefore prevent the increase of the copper ion from preventing rate of etch from reducing.
The specific example of the etching accelerator can include being selected from by nitric acid, sulfuric acid, boric acid, phosphoric acid, phosphorous acid, second
More than one of group that acid, phosphonic acids, sulfonic acid and the anion based on hydrochloric acid are formed, these etching accelerator can individually make
With or be used in mixed way two or more.
Relative to total 100 weight % etchant, the content of the etching accelerator can be for 0.1 weight % extremely
10 weight %, it is preferably 0.2 weight % to 7 weight %, more preferably 0.3 weight % to 5 weight %.If meet above-mentioned
Scope, then the copper film of appropriate amount can be etched, and there is excellent etching outline.It is less than in the content of the etching accelerator
During 0.1 weight %, etching speed reduces, and etching outline is deteriorated, and is also possible to produce residue, in the content of the etching accelerator
During more than 10 weight %, it may occur however that over etching, crackle occurs on the photoresist, etchant penetrates into the crackle
In, the problem of so as to occur exceedingly to etch the copper film being disposed below.
Chelating agent
The etchant of the present invention can also include chelating agent.
The chelating agent prevent want etching process metal wire quantity increase when etching solution in copper or metal from
Son increases so as to reduce the phenomenon of etch capabilities.
The specific example of the chelating agent can include being selected from by iminodiacetic acid, citric acid, ethanol acid derivative, poly-
It is more than one of group that ethylene glycol derivative, NTA and the nitrilo- pentaacetic acid of diethylidene three are formed.
Relative to total 100 weight % etchant, the content of the chelating agent can be 0.1 weight % to 7 weights
%, preferably 0.3 weight % to 6 weight %, more preferably 0.5 weight % are measured to 5 weight %, is less than in the content
During 0.1 weight %, it is impossible to the phenomenon that etch capabilities reduce when handling quantity increase is prevented, in the content more than 5 weight %
When, the problem of reaching the critical point no longer having an impact, and may be separated out because solubility is bad.
Cyclic amine compound
The etchant of the present invention can also include cyclic amine compound.
The cyclic amine compound plays a part of suppressing etching, and plays regulation etching speed and reduce the key of pattern
Size penalty (CD Loss, CD loss) is to improve the effect of process margin.
The cyclic amine compound can be that any cyclic amine compound used in the art limits without special, its
One example can be the azole compounds that carbon number is 1 to 30.More specifically example can be triazole class compounds, amino four
Azole compounds, alkyl tetrazole compound, glyoxaline compound, Benzazole compounds, purine compound, pyrazoles chemical combination
Thing, pyridine compounds and their, pyrimidines, azoles, pyrrolidines, pyrrolines, these
Cyclic amine compound may be used alone or in combination more than both.
The triazole class compounds for example can be l, 2,3 triazole, 5- methylbenzotrazoles, BTA, 1-
(2,2- dihydroxy ethyls) BTA, I-hydroxybenzotriazole, 1- methoxyl groups BTA, 1- (1,2- dihydroxypropyls) benzo
Triazole, 1- (2,3- dihydroxypropyl) BTA, double (the 2- ethylhexyls)-aryl methyl -1H- BTA -1- first of N, N-
Amine, 2,2'- { [(4- methyl isophthalic acid H- BTA -1- bases) methyl] imino group } di-methylcarbinol, 2,2'- { [(5- methyl isophthalic acid H- benzos
Triazol-1-yl) methyl] imino group di-methylcarbinol, 5- carboxyl benzotriazoles butyl ester, 5- carboxyl benzotriazoles monooctyl ester, 5- carboxyl benzos
Triazole dodecyl ester etc..These triazole class compounds may be used alone or in combination more than both.
The Aminotetrazole class compound for example can be Aminotetrazole, 5- Aminotetrazoles, 5- amino -1- phenyltetrazoles,
5- amino -1- (1- naphthyls) tetrazolium, 1- methyl -5- Aminotetrazoles, 1,5- diaminourea tetrazoliums etc..These Aminotetrazole class compounds
It may be used alone or in combination more than both.
The alkyl tetrazole compound is such as can be 5- methyl tetrazolium, 5- ethyls tetrazolium and 5- propyl tetrazols.This
A little alkyl tetrazole compounds may be used alone or in combination more than both.
The glyoxaline compound for example can be imidazoles, 2-methylimidazole, 2- ethyl imidazol(e)s, 2- propyl imidazoles, 2- ammonia
Base imidazoles, 4-methylimidazole, 4- ethyl imidazol(e)s, 4- propyl imidazoles etc..These glyoxaline compounds can be used alone or mix
Using more than both.
The Benzazole compounds for example can be aminoalkyl indole, benzoyl indoles, methyl indol, phenylacetyl group Yin
Diindyl, indolocarbazole etc..These Benzazole compounds may be used alone or in combination more than both.
The purine compound for example can be 6- dimethylaminopurines, the chloro- 7- methyl -7H- purine of 2,6- bis-, 6-
(γ, γ-Dimethylallylamino) purine, the chloro- 9H- purine -9- acetic acid of 2- amino -6- etc..These purine compounds can
To be used alone or be used in mixed way more than both.
The pyrazole compound for example can be 3- phenyl -1H- pyrazoles, 3- (amino methyl) pyrazoles, 5- (2- thiophene
Base) pyrazoles, 1- (2- ethoxys) pyrazoles, 3- (2- thienyls) pyrazoles, 5- methyl isophthalic acid H- pyrazoles, 4- nitro -1H- pyrazoles, 1H- pyrroles
Azoles -5- boric acid etc..These pyrazole compounds may be used alone or in combination more than both.
The pyridine compounds and their can be for example 4- (amino-ethyl) pyridine, 2- (methylamino) pyridine, pyridine trifluoro
Acetate, pyridine -4- acetamides, 2 [(pyridine -3- carbonyls)-amino]-benzoic acid etc..These pyridine compounds and theirs can be independent
Using or be used in mixed way more than both.
The pyrimidines are such as can be pyrimidine -5-carboxylic acid, pyrimidine -2- carboxylic acids.These pyrimidines
It may be used alone or in combination more than both.
The azoles for example can be pyrroles -2- carboxylic acids, pyrroles -3- carboxylic acids, 1- (2- aminophenyls) pyrroles,
1H- pyrroles's -1- propionic acid etc..These azoles may be used alone or in combination more than both.
The pyrrolidines for example can be 1- (2- amino-ethyls) pyrrolidines, pyrrolidines -3- carboxylic acids, pyrroles
Alkane -3- carboxylic acid hydrochlorides, pyrrolidines -1,2- dicarboxylic acids 1- phenyl esters etc..These pyrrolidines can be used alone or mix
Close using more than both.
The pyrrolines for example can be 3- pyrrolins, 2- methyl isophthalic acids-pyrrolin, 1- benzyl -3- pyrrolins
Deng.These pyrrolines may be used alone or in combination more than both.
In the uniform etching and etching speed of regulation copper film and control etches pretilt angle so that it is even in processing number
It will not also increase when amount accumulation and keep constant aspect, preferably using alkyl tetrazolium, more preferably use 5- methyl tetrazoliums.
Relative to the etchant for copper base metal film, the content of the cyclic amine compound can be 0.05 weight
Part is measured to 4 parts by weight, preferably 0.07 parts by weight to 3 parts by weight, more preferably 0.1 parts by weight to 2 parts by weight.It is it is preferred that described
Cyclic amine compound is lost in the scope with can suitably adjust etching speed and reduce the CD of pattern.
Fluorochemical
The etchant of the present invention can also include fluorochemical.
The fluorochemical refers to dissociating in water to generate the compound of fluorine ion, with hydrogen peroxide together
To etch the main component of copper base metal film, necessarily produced when can be readily removable etching at the same time and molybdenum or molybdenum alloy film
Raw residue.
The fluorochemical is not particularly limited, as long as it can be fluorine ion or polyatom fluorine in solution internal disintegration
Ion, such as can be ammonium fluoride, sodium fluoride, potassium fluoride, ammonium acid fluoride, sodium bifluoride, potassium hydrogen fluoride etc., these fluorine-containing chemical combination
Thing may be used alone or in combination more than both.
The content of the fluorochemical is had no particular limits, for example, relative to the gross weight of etchant,
The content of the fluorochemical can be 0.01 weight % to 1 weight %, be preferably 0.05 weight % to 0.25 weight %.
When the content of the fluorochemical is 0.01 weight % to 1 weight %, appropriate etching speed is shown, it is taken as that can
Easily control technique.Especially, etching and molybdenum or during molybdenum alloy film at the same time, can effectively suppress etch residue life
Into.In addition, when the content of the fluorochemical is more than 1 weight %, the rate of etch raising of glass substrate may also occur
Problem.
Water
The etchant of the present invention can also include water.
The water is not particularly limited, can preferably use deionized water, more preferably uses and is used as semiconductor technology
The ratio resistance value of deionized water is 18M Ω/more than cm water.
The content of the water can be the surplus relative to total 100 weight % etchant.
In addition to mentioned component, etchant of the invention can also include common additive.For example, additive
Can be to etch conditioning agent, metal ion block agent, preservative, surfactant, pH adjusting agent etc., but not limited to this.
<Metal film engraving method>
In addition, the present invention relates to the method for etching copper base metal film, including：Step i) forms copper base metal on substrate
Film；Step ii) on the copper base metal film light reaction material is optionally set；And step iii) utilize the erosion of the present invention
Liquid composition is carved to be etched the copper base metal film exposed.
In the method for the etching copper base metal film of the present invention, the light reaction material is preferably common photoresist
Material, and can optionally be remained by common exposed and developed technique.
<Array substrate for liquid crystal display device manufacture method>
In addition, the present invention relates to array substrate for liquid crystal display device manufacture method, including：Step a) is formed on substrate
Gate line；Step b) forms gate insulator on the substrate including the gate line；Step c) is on the gate insulator
Form semiconductor layer；Step d) forms source class and drain line on the semiconductor layer；And step e) forms pixel electrode, institute
Pixel electrode is stated to be connected with the drain line.
The step a) includes：Copper base metal film is formed on substrate and using etchant of the invention to described
The step of copper base metal film is etched to form gate line.
The step d) includes：Form copper base metal film and using etchant of the invention to the copper base metal
The step of film is etched to form source class and drain line.
The array substrate for liquid crystal display device can be thin film transistor (TFT) (TFT) array base palte.
Hereinafter, in order to help to understand invention shows preferred embodiment, but it should be apparent to a person skilled in the art that
Following embodiments are only used for illustrating the present invention, in the range of the technological thought of the present invention, can carry out various changes to the present invention
Type and modification, these variants and modifications should be included within the scope of the appended claims.In the case where being not specifically stated, under
State and represent that " % " and " part " of content is based on weight in embodiment and comparative example.
Embodiment 1,2 and comparative example 1,2：The preparation of etchant
The composition shown in table 1 below is mixed with corresponding content, to prepare etchant.
[table 1]
Experimental example：Quantity is handled to assess
Carried out using the etchant prepared in above-described embodiment 1,2 and comparative example 1,2 with reference to etching
(reference etch) is tested, and with reference to testing addition copper powder 1000ppm in etching solution and being completely dissolved it, is confirmed repeatedly
The process of etching speed, cone angle and side etching quantity.By above-mentioned three kinds of etching characteristics compared with etching test initial stage, observing
During more than 10% change, the amount of copper added before is evaluated as to handle quantity.
[table 2]
| (unit:ppm) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Handle quantity | 7000 | 10000 | 8000 | 3000 | 4500 |
Confirmed with reference to above-mentioned table 2, compared to not comprising lewis acidic situation (comparative example 1 and 2), of the invention includes road
The processing quantity of the etchant (Examples 1 and 2) of Lewis acid is more excellent.
Claims (10)
1. a kind of etchant for copper base metal film, the etchant includes lewis acid.
2. the etchant according to claim 1 for copper base metal film, it is characterised in that described for copper-based
The etchant of metal film also includes being selected from by metal film oxidant, etching accelerator, cyclic amine compound and chelating agent
It is more than one of group formed.
3. the etchant according to claim 1 for copper base metal film, it is characterised in that the lewis acid
Including selected from by Zn2+、Al3+、Fe3+、Sn4+And Zr2+One or more of group formed metal ion.
4. the etchant according to claim 2 for copper base metal film, it is characterised in that the metal film oxygen
Agent is more than one of group being made up of persulfate and hydrogen peroxide.
5. the etchant according to claim 2 for copper base metal film, it is characterised in that the etching promotes
Agent includes one in the group being made up of phosphoric acid, phosphorous acid, phosphonic acids, sulfuric acid, sulfonic acid, acetic acid and anion based on hydrochloric acid
It is more than person.
6. the etchant according to claim 2 for copper base metal film, it is characterised in that the ring-type amination
Compound includes 5- methyl tetrazoliums.
7. the etchant according to claim 2 for copper base metal film, it is characterised in that the chelating agent bag
Include selected from one of group for being made up of iminodiacetic acid, citric acid, ethanol acid derivative and polyethyleneglycol derivative with
On.
8. the etchant according to claim 2 for copper base metal film, it is characterised in that described for copper-based
The etchant of metal film also includes fluorochemical.
9. a kind of method for etching copper base metal film, including：
Step i), copper base metal film is formed on substrate；
Step ii), light reaction material is optionally set on the copper base metal film；And
Step iii), utilize the etchant pair according to any one of claim 1 to 8 for copper base metal film
The copper base metal film exposed is etched.
10. a kind of method for manufacturing array substrate for liquid crystal display device, methods described include：
Step a), forms gate line on substrate；
Step b), gate insulator is formed on the substrate including the gate line；
Step c), semiconductor layer is formed on the gate insulator；
Step d), source class line and drain line are formed on the semiconductor layer；And
Step e), pixel electrode being formed, the pixel electrode is connected with the drain line,
Wherein, the step a) includes：Copper base metal film is formed on substrate and using according to any one of claim 1 to 8
The step of described etchant for copper base metal film is etched to form gate line to the copper base metal film,
The step d) includes：Form copper base metal film and utilize copper base metal according to any one of claim 1 to 8
The step of etchant of film is etched to form source class line and drain line to the copper base metal film.
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| KR10-2016-0066373 | 2016-05-30 | ||
| KR1020160066373A KR101980333B1 (en) | 2016-05-30 | 2016-05-30 | Etchant composition for copper-containing metal layer and preparing method of an array substrate for liquid crystal display using same |
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Cited By (3)
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| CN111020587A (en) * | 2019-12-23 | 2020-04-17 | 周兆梅 | Deplating liquid for removing nickel layer on copper surface and deplating process thereof |
| CN111663138A (en) * | 2020-07-08 | 2020-09-15 | 江苏和达电子科技有限公司 | Etching solution for copper-containing laminated film of liquid crystal panel and application thereof |
| CN115678437A (en) * | 2022-11-04 | 2023-02-03 | 河北工业大学 | Hydrogen peroxide system weak acid based molybdenum barrier layer chemical mechanical polishing solution and preparation method thereof |
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| KR102642371B1 (en) * | 2019-03-29 | 2024-03-04 | 동우 화인켐 주식회사 | Etchant composition for etching for copper-based metal layer and method of etching using the same |
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| KR102150523B1 (en) * | 2014-01-28 | 2020-09-01 | 동우 화인켐 주식회사 | Etching solution composition for copper layer and titanium layer and method of preparing array substrate for liquid crystal display using the same |
| KR102419970B1 (en) | 2014-06-30 | 2022-07-14 | 솔브레인 주식회사 | Composision for etching, method for etching and electronic device |
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| US20130034923A1 (en) * | 2011-08-05 | 2013-02-07 | Samsung Electronics Co., Ltd. | Etching composition, method of forming a metal pattern using the etching composition, and method of manufacturing a display substrate |
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| CN111020587A (en) * | 2019-12-23 | 2020-04-17 | 周兆梅 | Deplating liquid for removing nickel layer on copper surface and deplating process thereof |
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| CN111663138A (en) * | 2020-07-08 | 2020-09-15 | 江苏和达电子科技有限公司 | Etching solution for copper-containing laminated film of liquid crystal panel and application thereof |
| CN115678437A (en) * | 2022-11-04 | 2023-02-03 | 河北工业大学 | Hydrogen peroxide system weak acid based molybdenum barrier layer chemical mechanical polishing solution and preparation method thereof |
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| KR20170135068A (en) | 2017-12-08 |
| CN107447215B (en) | 2021-06-22 |
| KR101980333B1 (en) | 2019-05-20 |
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