CN107988598A - The manufacture method of etchant and array substrate for display device - Google Patents

The manufacture method of etchant and array substrate for display device Download PDF

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Publication number
CN107988598A
CN107988598A CN201711262782.6A CN201711262782A CN107988598A CN 107988598 A CN107988598 A CN 107988598A CN 201711262782 A CN201711262782 A CN 201711262782A CN 107988598 A CN107988598 A CN 107988598A
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weight
etchant
film
metal
metal film
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CN107988598B (en
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李恩远
朴升煜
田玹守
梁承宰
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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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
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • 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
    • 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
    • C23F1/18—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
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/26—Acidic compositions for etching refractory metals
    • 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
    • C23F1/32—Alkaline compositions
    • C23F1/34—Alkaline compositions for etching copper or alloys thereof
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1259—Multistep manufacturing methods

Abstract

The present invention relates to etchant, the manufacture method of array substrate for display device and array substrate for display device, more specifically, there is provided when manufacturing array substrate for display device, metal film can be etched in the lump, the etchant of metal film, the manufacture method of array substrate for display device and the array substrate for display device of the excellent characteristic of the etching outline of interface portion when there is etching speed, cone angle excellent and etching multilayer film.The etchant of the metal film is characterized in that, relative to composition total weight, comprising：5~25 weight % of hydrogen peroxide, 0.01~1 weight % of fluorine compounds, 0.1~5 weight % of azole compounds, intramolecular have the water of 0.1~5 weight % of water soluble compound of nitrogen-atoms and carboxyl, 0.001~5 weight % of phosphate comprising alkali or alkaline earth metal, 0.01~5 weight % of EPE polyol EPE, 0.1~5 weight % of sulfate comprising alkali or alkaline earth metal and surplus, and the weight ratio of phosphate and sulfate is 1:3~1:20.

Description

The manufacture method of etchant and array substrate for display device
Technical field
The present invention relates to the manufacture method of etchant and array substrate for display device.
Background technology
In semiconductor device, on substrate formed metal wiring process generally include to utilize following process the step of：Profit With the metal film formation process of sputtering etc.；It is coated with using photoresist, is in exposed and developed selective area photic anti- Lose agent formation process；And etching work procedure, and it is included in cleaning process before and after Individual cells process etc..Such etching work procedure Refer to, using photoresist as mask, the process that metal film is left in selective area is usually used to utilize plasma Deng dry-etching or using etchant Wet-type etching.
In such semiconductor device, the resistance of metal wiring is primarily upon in recent years.This is because resistance is to induce RC The principal element of signal delay, particularly in Thin Film Transistor-LCD (thin film transistor-liquid Crystal display, TFT-LCD) in the case of, the increase of panel size and high-resolution realization are increasingly becoming technological development Key.Therefore, in order to realize subtracting for necessary RC signal delays in the maximization of the display device including TFT-LCD etc. It is few, it is necessary to develop low resistance material.Therefore, actual conditions are to lead chromium (Cr, resistivity to be used in the past：12.7×10-8Ω M), molybdenum (Mo, resistivity：5×10-8Ω m), aluminium (Al, resistivity：2.65×10-8Ω m) and their alloy be difficult to use in greatly Gate wirings and data wiring used in the display devices such as type TFT-LCD etc..
In this context, as new low resistive metal film, the copper system metal film such as copper film and copper-molybdenum film is paid high attention to And its etchant, and this is actively studied.For example, in KR published patent the 2010-0090538th Disclose has nitrogen-atoms comprising hydrogen peroxide, organic acid, phosphate compounds, water-soluble cyclic amine compound, an intramolecular The etching solution group of the copper system metal film of water soluble compound, fluorochemical, EPE polyol EPE and water with carboxyl Compound.However, for above-mentioned etching solution, deposited in terms of the cone angle maintenance that number ongoing change is handled in etching of thick film metal layer Limiting to, interface portion produces the problem of corroding when having etching multilayer film.
Prior art literature
Patent document
Patent document 1：KR published patent the 2010-0090538th
The content of the invention
Problem to be solved
It is an object of the present invention to provide metal film etching speed and cone angle excellent and when etching multilayer film There is no the erosion of interface portion and etching outline is excellent, will not produce the etchant of the metal film of residue.
The method for solving problem
To achieve these goals, the present invention provides a kind of etchant of metal film, it is characterised in that relative to Composition total weight, comprising：5~25 weight % of hydrogen peroxide, 0.01~1 weight % of fluorine compounds, azole compounds 0.1~5 Weight %, an intramolecular have 0.1~5 weight % of water soluble compound of nitrogen-atoms and carboxyl, include alkali metal or alkaline earth 0.001~5 weight % of phosphate of metal, 0.01~5 weight % of EPE polyol EPE, include alkali metal or alkaline earth gold 0.1~5 weight % of sulfate of category and the water of surplus,
The weight ratio of above-mentioned phosphate and sulfate is 1:3~1:20.
In one embodiment, above-mentioned metal film can be copper system metal film.
In another embodiment, above-mentioned copper system metal film can be the monofilm of copper or copper alloy or be multilayer film, institute State multilayer film and include the film selected from one or more of the group being made of molybdenum film, molybdenum alloy film, titanium film and titanium alloy film, Yi Jixuan From the film of one or more of copper film and tin-copper alloy film.
In addition, the present invention provides a kind of manufacture method of array substrate for display device, it is characterised in that including：A) exist On substrate formed gate wirings the step of, b) on the substrate comprising above-mentioned gate wirings formed gate insulator the step of, c) On above-mentioned gate insulator formed semiconductor layer the step of, d) on above-mentioned semiconductor layer formed source electrode and drain electrode step Suddenly the step of and e) forming the pixel electrode being connected with above-mentioned drain electrode,
Above-mentioned a) step or d) at least one step in step be included on aforesaid substrate be laminated metal layer the step of, with And the step of being etched using etchant,
Above-mentioned etchant is included relative to composition total weight：5~25 weight % of hydrogen peroxide, fluorine compounds 0.01~1 weight %, 0.1~5 weight % of azole compounds, an intramolecular have the water soluble compound of nitrogen-atoms and carboxyl 0.1~5 weight %, 0.001~5 weight % of phosphate, EPE polyol EPE comprising alkali or alkaline earth metal The water of 0.01~5 weight %, 0.1~5 weight % of sulfate comprising alkali or alkaline earth metal and surplus,
The weight ratio of above-mentioned phosphate and sulfate is 1:3~1:20.
Above-mentioned metal layer can be the metal layer comprising copper or copper alloy.
In addition, the present invention provides a kind of array substrate for display device, it includes the etching solution group using above-mentioned metal film Compound etches one or more of the gate wirings formed, source electrode and drain electrode.
Invention effect
The etchant of the present invention is capable of providing following effect：, can when manufacturing array substrate for display device Interface when metal film is etched in the lump, cone angle, the lateral erosion variable quantity excellent with processing substrate number, and etch multilayer film The etching outline in portion is excellent.
Brief description of the drawings
Fig. 1 be evaluation using embodiment 1 etchant etching Cu/MoNb duplicatures after (a) etching section, (b) SEM photograph that etching outline and residue the presence or absence of produce.
Fig. 2 is invaded for generation interface portion after confirming the etchant etching Cu/MoNb duplicatures using comparative example 4 The SEM photograph of erosion.
Fig. 3 is for producing residue after confirming the etchant etching Cu/MoNb duplicatures using comparative example 6 SEM photograph.
Embodiment
The display device of etchant the present invention relates to metal film and the etchant using the metal film With the manufacture method of array base palte.
The present inventor in order to provide have etch metal film when etching speed and cone angle it is excellent and etching multilayer There is no interface portion to corrode during film during the etchant of the excellent effect of etching outline is furtherd investigate, confirm To containing the water that hydrogen peroxide, fluorine compounds, azole compounds, intramolecular have nitrogen-atoms and carboxyl with certain content Soluble compound, phosphate, EPE polyol EPE, sulfate and water and with the weight ratio in particular range include it is above-mentioned In the case of phosphate and sulfate, there can be the effect above, so as to complete the present invention.
Hereinafter, the present invention will be described in detail.
The present invention provides a kind of etchant of metal film, it is characterised in that relative to composition total weight, bag Contain：5~25 weight % of hydrogen peroxide, 0.01~1 weight % of fluorine compounds, 0.1~5 weight % of azole compounds, a molecule Interior 0.1~5 weight % of water soluble compound, the phosphate comprising alkali or alkaline earth metal with nitrogen-atoms and carboxyl 0.001~5 weight %, 0.01~5 weight % of EPE polyol EPE, the sulfate comprising alkali or alkaline earth metal The water of 0.1~5 weight % and surplus,
The weight ratio of above-mentioned phosphate and sulfate is 1:3~1:20.It is highly preferred that contained above-mentioned phosphate and sulfuric acid The weight ratio of salt can be 1:5~1:10.
In the case where the weight ratio of above-mentioned phosphate and sulfate is in above range, can realize excellent cone angle and The etching speed of metal film.
It is less than 1 in the weight ratio of the phosphate in terms of said reference and sulfate:In the case of 3, etching speed is insufficient and nothing Method realizes sufficiently etching, it is possible to create the problem of cone angle becomes larger, more than 1:In the case of 20, etching speed is too fast and is not easy Control process, and more than 55 ° to produce etching outline bad for cone angle.
In the present invention, above-mentioned metal film can be copper system metal film, and above-mentioned copper system metal film wraps in the constituent of film Cupric, can be the concept of the monofilm and multilayer film that include copper or copper alloy, and the multilayer film is included to be closed selected from copper film and copper The film of one or more of golden film and in the group being made of molybdenum film, molybdenum alloy film, titanium film and titanium alloy film it is a kind of with On film.
In addition, the concept of above-mentioned so-called alloy film further includes nitride film or oxide-film.
As the example of above-mentioned multilayer film, copper/molybdenum film, copper/molybdenum alloy film, copper alloy/molybdenum alloy film, copper/titanium can be enumerated The duplicatures such as film or trilamellar membrane.Above-mentioned copper/molybdenum film means the layers of copper formed comprising molybdenum layer and on above-mentioned molybdenum layer, on State copper/molybdenum alloy film and mean the layers of copper formed comprising Mo alloy and on above-mentioned Mo alloy, copper alloy/molybdenum alloy film Mean the copper alloy layer formed comprising Mo alloy and on above-mentioned Mo alloy, above-mentioned copper/titanium film, which is meant, to be included Titanium layer and the layers of copper formed on above-mentioned titanium layer.
Above-mentioned copper alloy layer refers to the layer formed by the alloy of following metal and copper, and the metal is selected from by such as aluminium (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver-colored (Ag), chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), one or more of group of composition such as hafnium (Hf), tantalum (Ta) and tungsten (W).
Above-mentioned Mo alloy refers to the layer formed by the alloy of following metal and molybdenum, and the metal is selected from by such as titanium (Ti), one or more of group of composition such as niobium (Nb), tungsten (W), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd) and indium (In).
Particularly, etchant of the invention is preferably applied to be formed by copper or tin-copper alloy film and molybdenum or molybdenum alloy film Multilayer film, above-mentioned multilayer film can be etched in the lump.
Hereinafter, the composition for the etchant that the present invention will be described in detail.
Hydrogen peroxide
Hydrogen peroxide (H included in the etchant of the present invention2O2) it is that etching to copper system metal film produces shadow Loud primary oxidant, above-mentioned copper system metal film can include the copper metal film formed on molybdenum alloy film and above-mentioned molybdenum alloy film.
Above-mentioned hydrogen peroxide (H2O2) be characterized in that, relative to composition total weight, its content is 5~25 weight %, more Preferably 17~23 weight %.In the case where content is less than 5 weight % in terms of said reference, it is possible to occur because of copper system metal The etch capabilities of film and/or molybdenum alloy film deficiency and the problem of can not realize sufficient etching.On the other hand, in content more than 25 In the case of weight %, etching speed integrally accelerates, therefore, it is difficult to control process, based on the increased fever of copper ion in composition Stability may substantially reduce.
Fluorine compounds
Fluorine compounds included in the etchant of the present invention are to refer to dissociate in water and discharge fluorine ion (F-) compound.Above-mentioned fluorine compounds are the pro-oxidants that influence is played on the etching speed of molybdenum alloy film, adjust molybdenum alloy The etching speed of film.
In addition, play the effect for removing the residue necessarily led in the solution of etching and molybdenum film at the same time.
Above-mentioned fluorine compounds are characterized in that, relative to the composition total weight of the present invention, its content is 0.01~1 weight Measure %, more preferably 0.05~0.2 weight %., may in the case where the content of above-mentioned fluorine compounds is less than 0.01 weight % Produce the etch residue of metal film.On the other hand, in the case where content is more than 1 weight %, there are the change of glass substrate etching rate The shortcomings that big.
Above-mentioned fluorine compounds are the fluorine compounds used in the art, as long as fluorine ion can be dissociateed in the solution Or the compound of polyatom fluorine ion, just it is not particularly limited.As the preferable concrete example of above-mentioned fluorine compounds, can enumerate HF、NaF、NH4F、NH4BF4、NH4FHF、KF、KHF2、AlF3And HBF4Deng, preferably using selected from it is therein more than one.
Azole compounds
The present invention etchant included in azole compounds play adjust copper system metal film etching speed, Reduce the CD losses (CD Loss) of pattern and improve the effect of the surplus in process.
Above-mentioned azole compounds are characterized in that, relative to composition total weight, its content is 0.1~5 weight %, more excellent Elect 0.3~0.8 weight % as.In the case where the content of the azole compounds in terms of said reference is less than 0.1 weight %, copper film etc. The etching speed of metal film is too fast and there may be excessive CD losses.On the other hand, in the case of more than 5 weight %, copper film Excessively slow and molybdenum alloy film the etching speed of etching speed Deng metal film is relatively excessively slow, thus the loss of activity time occurs, residual Staying the possibility of the residue of molybdenum alloy increases.
As long as above-mentioned azole compounds azole compounds usually used in this field are just not particularly limited, but can be with The more preferably azole compounds of carbon number 1~30.It can more preferably use selected from triazole (triazole) based compound, ammonia Base tetrazolium (aminotetrazole) based compound, imidazoles (imidazole) based compound, indoles (indole) based compound, Purine (purine) based compound, pyrazoles (pyrazol) based compound, pyridine (pyridine) based compound, pyrimidine (pyrimidine) based compound, pyrroles (pyrrole) based compound, pyrrolidines (pyrrolidine) based compound and pyrroles One or more of quinoline (pyrroline) based compound etc. compound.
One intramolecular has the water soluble compound of nitrogen-atoms and carboxyl
An intramolecular has the water-soluble chemical combination of nitrogen-atoms and carboxyl included in the etchant of the present invention Thing prevents the selfdecomposition for the hydrogen peroxide that may occur during keeping etchant, and is etched to substantial amounts of substrate When prevent etching characteristic from changing.In general, using hydrogen peroxide etchant in the case of, keeping when by In hydrogen peroxide generation selfdecomposition, its storage time is not grown, and also tool is there is a possibility that the hazards of container explosion.But wrapping In the case that intramolecular containing said one has the water soluble compound of nitrogen-atoms and carboxyl, the decomposition rate of hydrogen peroxide reduces Nearly 10 times, so that it is advantageously ensured that storage time and stability.
Particularly, in the case of layers of copper, when copper ion is largely remained in etchant, may relatively mostly occur shape Into the situation for being passivated (passivation) film and being no longer etched after oxidizing blackening, but in the case where adding above-claimed cpd, It can prevent this phenomenon.
The water soluble compound that said one intramolecular has nitrogen-atoms and carboxyl is characterized in that, relative to the present invention's Composition total weight, its content are 0.1~5 weight %, more preferably 1.5~3.0 weight %.Have in said one intramolecular In the case that the content of the water soluble compound of nitrogen-atoms and carboxyl is less than 0.1 weight %, substantial amounts of substrate (about 500) is etched After can form passivating film and be difficult to obtain sufficient operation allowance.On the other hand, said one intramolecular have nitrogen-atoms and In the case that the content of the water soluble compound of carboxyl is more than 5 weight %, the etching speed of molybdenum or molybdenum alloy is slack-off, it is thus possible to The problem of generation etching copper-molybdenum film or the cone angle of copper-molybdenum alloy film diminish.
There is the concrete example of the water soluble compound of nitrogen-atoms and carboxyl as said one intramolecular, alanine can be enumerated (alanine), aminobutyric acid (aminobutyric acid), glutamic acid (glutamic acid), glycine (glycine), Iminodiacetic acid (iminodiacetic acid), nitrilotriacetic acid (nitrilotriacetic acid) and methyl amimoacetic acid (sarcosine) etc., can use selected from it is therein more than one.
Phosphate comprising alkali or alkaline earth metal
Phosphate (- PO included in the etchant of the present invention4 3-) play and make cone angle profile and the etching of pattern The good effect of profile.
Above-mentioned the phosphate (- PO comprising alkali or alkaline earth metal4 3-) it is one or two hydrogen in phosphoric acid by alkali metal Or the phosphate that alkaline-earth metal displacement forms, as concrete example, sodium dihydrogen phosphate (sodium phosphate can be enumerated Monobasic), potassium dihydrogen phosphate (potassium phosphate monobasic), disodium hydrogen phosphate (sodium Phosphate dibasic) and dipotassium hydrogen phosphate (potassium phosphate dibasic) etc., it can use and be selected from it One or more of.
It is above-mentioned it is phosphatic be characterized in that, relative to the present invention composition total weight, its content is 0.001~5 weight Measure %, more preferably 0.05~0.3 weight %.In situation of the phosphatic content less than 0.001 weight % in terms of said reference Under, etching outline may be bad.On the other hand, in the case where its content is more than 5 weight %, it may occur however that the erosion of molybdenum alloy film The problem of quarter slows.
EPE polyol EPE
The present invention etchant included in EPE polyol EPE play make surface tension reduce and Improve the effect of etch uniformity.In addition, above-mentioned EPE polyol EPE by surround after the metal films such as etching Copper ion of dissolution etc. in etching solution, so as to suppress the activity of copper ion, suppresses the decomposition reaction of hydrogen peroxide.If so drop The activity of low copper ion, then can stably carry out process during etching solution is used.
Above-mentioned EPE polyol EPE is characterized in that, relative to the composition total weight of the present invention, its content is 0.01~5 weight %, more preferably 2.0~5.0 weight %.It is less than 0.01 weight in the content of above-mentioned EPE polyol EPE In the case of measuring %, it may occur however that the problem of etch uniformity reduces, the decomposition of hydrogen peroxide is accelerated.On the other hand, contain at it In the case that amount is more than 5 weight %, there is the shortcomings that producing a large amount of foams.
Above-mentioned EPE polyol EPE can be preferably using selected from glycerine (glycerol), ethylene glycol (ethylene Glycol), diethylene glycol (diethylene glycol), triethylene glycol (triethylene glycol) and polyethylene glycol One or more of (polyethylene glycol) etc., but be not limited to this.
Sulfate comprising alkali or alkaline earth metal
Sulfate, which plays, included in the etchant of the present invention makes the good effect of the cone angle profile of pattern, and Play the effect for adjusting the etching speeds of metal film such as copper film.
The above-mentioned sulfate comprising alkali or alkaline earth metal is one or two hydrogen in sulfuric acid by alkali metal or alkaline earth The sulfate that metal replacement forms, as concrete example, can use selected from sodium sulphate (sodium sulfate), potassium sulfate (potassium sulfate), niter cake (sodium hydrogensulfate) and potassium acid sulfate (potassium One or more of hydrogensulfate) etc., but be not limited to this.
Above-mentioned sulfate is characterized in that, relative to the composition total weight of the present invention, its content is 0.1~5 weight %, More preferably 0.5~4 weight %.In the case where the content of the sulfate in terms of said reference is less than 0.1 weight %, metal film Etch capabilities are insufficient and possibly can not realize sufficient etching, and are possible to generation processing number and evaluate the etching characteristic such as bad not It is good.On the other hand, above-mentioned sulfate content more than 5 weight % in the case of, because of the too fast and unmanageable work of etching speed Sequence, the process that can not be stablized.
Water
The content of water is composition total weight is become 100 weight % included in the etchant of the present invention Surplus.Above-mentioned water is not particularly limited, preferably using deionized water.In addition, more preferably degree is removed using embodiment water intermediate ion Water resistivity value be more than 18M Ω cm deionized water.
In addition, the etchant of the present invention can further include common additive in addition to mentioned component. As above-mentioned additive, sequestering agent, anticorrosive etc. can be enumerated, but is not limited to this, in order to make the effect of the present invention more Well, other additives well known in the art can be further included.But in the case where further including tartaric acid, Ke Nengfa It is raw to separate out therefore not preferred.
Component included in the etchant of the present invention preferably has the purity for semiconductor process.
In addition, as one embodiment of the invention, there is provided a kind of method for forming wiring, it includes：
1) on substrate formed molybdenum alloy film the step of；
2) on above-mentioned molybdenum alloy film formed copper system metal film the step of；
3) optionally leave light reaction material on above-mentioned copper system metal film the step of；And
4) the step of above-mentioned copper system metal film and molybdenum alloy film being etched in the lump using the etchant of the present invention.
Above-mentioned light reaction material is preferably common photoresist, can be selected by common exposed and developed process Leave to selecting property.
In addition, the present invention provides a kind of manufacture method of array substrate for display device, it is characterised in that including：
A) on substrate formed gate wirings the step of,
B) on the substrate comprising above-mentioned gate wirings formed gate insulator the step of,
C) on above-mentioned gate insulator formed semiconductor layer the step of,
D) on above-mentioned semiconductor layer formed source electrode and drain electrode the step of and
E) the step of forming the pixel electrode being connected with above-mentioned drain electrode,
Above-mentioned a) step or d) at least one step in step be included on aforesaid substrate be laminated metal layer the step of, with And the step of being etched using etchant,
Above-mentioned etchant is included relative to composition total weight：5~25 weight % of hydrogen peroxide, fluorine compounds 0.01~1 weight %, 0.1~5 weight % of azole compounds, an intramolecular have the water soluble compound of nitrogen-atoms and carboxyl 0.1~5 weight %, 0.001~5 weight % of phosphate, EPE polyol EPE comprising alkali or alkaline earth metal The water of 0.01~5 weight %, 0.1~5 weight % of sulfate comprising alkali or alkaline earth metal and surplus,
The weight ratio of above-mentioned phosphate and sulfate is 1:3~1:20.
Above-mentioned metal layer can be the metal layer comprising copper or copper alloy.
Above-mentioned display device can be liquid crystal display device or OLED etc., but be not limited to this, etching solution group of the invention For compound due to that will not produce residue in etching, there is no the bad problem of electrical short or distribution, can be realized in manufacture Big picture, high brightness circuit array substrate for display device when be efficiently used.
Above-mentioned array substrate for display device can be thin film transistor (TFT) (TFT) array base palte.
In addition, the etchant of the present invention can etch gate wirings, source electrode and drain electrode in the lump, the present invention One kind in the gate wirings formed comprising the etchant etching using above-mentioned metal film, source electrode and drain electrode is provided Array substrate for display device above.
Hereinafter, the present invention is described in more detail using embodiment, comparative example and experimental example.However, following embodiments, comparing Example and experimental example are used to illustrate the present invention, therefore the present invention is from the restriction of following embodiments, comparative example and experimental example, Ke Yijin The diversified modifications and changes of row.
<Embodiment and comparative example>
The manufacture of 1~8. etchant of embodiment 1~9 and comparative example
Composition and content (weight %) as described in table 1 below, manufacture etchant 180kg.
[table 1]
Note) in above-mentioned table 1,
NHP：Sodium dihydrogen phosphate
PPM：Potassium dihydrogen phosphate
APM：Ammonium phosphate
SS：Sodium sulphate
PS：Potassium sulfate
AS：Ammonium sulfate
TEG：Triethylene glycol (triethylene glycol)
Phosphite：Sodium phosphite (sodium phosphite)
<Experimental example>The etching characteristic evaluation of etchant
Respectively using embodiment 1~9 and the etchant of comparative example 1~8, implement etching work procedure.Utilize injecting type Experimental facilities (the model name of etching mode：ETCHER (TFT), SEMES companies), the temperature of etchant in etching work procedure It is set to about 33 DEG C or so.Etching period can be different according to etch temperature, but are usually carried out with 110 seconds or so.Use SEM (Hitachi, Ltd's product, model name S-4700) detects the section of outline of the copper system metal film etched in above-mentioned etching work procedure, will As a result it is documented in table 2 below.
The test piece (Cu/MoNb) used in etching work procedure has used following test piece：At glass substrate (Ⅹ 100mm of 100mm) Upper evaporation molybdenum-niobium alloy film, after copper film is deposited on above-mentioned film, by photoetching (photolithography) process, in substrate It is upper to form the photoresist with predetermined pattern.
1. etching speed of experimental example is evaluated
Naked eyes measure endpoint detecting (End Point Detection, EPD), obtain different time etching speed (E/R, Etch Rate), etching speed is only evaluated with the etching speed of longitudinal direction.If by the thickness of the metal film etched Divided by EPD, then it can obtain (time) per second(thickness)Etching speed, evaluated by following benchmark, and will The results are shown in table 2.
<Cu etching speed metewands>
○：Well
Х：Difference (is less thanOr exceed)
Unetch：It can not etch
2. cone angle of experimental example (Taperangle, °) evaluation
Cone angle (Taper angle) refers to the gradient on copper (Cu) inclined-plane.Cone angle is excessive or too small, can be steamed in subsequent film Occur to be become by bad caused crackle (crack) phenomenon of Step Coverage (step coverage) or subsequent film evaporation during plating Difficulty, therefore it is critically important to maintain suitable cone angle.In this evaluation, evaluated by following benchmark, and the results are shown in Table 2.
<Cone angle metewand>
○：Well (45~55 °)
Х：Difference (is less than 45 ° or more than 55 °)
3. interface portion erosion assessment of experimental example
It is put into above-mentioned sample to start to spray, if reaching the etching period of 110 seconds, takes out and cleaned with deionized water, Then it is dried using drying device, photoresist is removed using photoresist stripping machine (PR stripper).Cleaning After drying, scanning electron microscope (SEM, model name are utilized：SU-8010, Hitachi, Ltd manufacture), confirm copper film (Cu) and Whether the erosion of molybdenum-niobium film (MoNb) interface portion produces, and show the result in table 2 below.
Nothing：Erosion is not produced
It can not confirm：Whether not being etched and can not confirm to corrode
4. residue of experimental example is evaluated
It is put into above-mentioned sample to start to spray, if reaching the etching period of 110 seconds, takes out and cleaned with deionized water, Then it is dried using drying device, photoresist is removed using photoresist stripping machine (PR stripper).Cleaning After drying, scanning electron microscope (SEM, model name are utilized：SU-8010, Hitachi, Ltd's manufacture), measure molybdenum-niobium is not eclipsed Phenomenon, the i.e. residue carved and left, is evaluated by following benchmark, and shows the result in table 2 below.
Nothing：Do not produce residue
It can not confirm：Whether not being etched and can not confirm that residue produces
Lateral erosion (Sideetch, S/E) variable quantity evaluation of the experimental example 5. based on processing substrate number
Lateral erosion (μm) variable quantity that measure changes with Cu ion concentrations (300~4,000ppm).Lateral erosion (Side etch, S/ E the distance between the side photoresist end that measures and lower metal end after etching) are referred to.If side etching quantity changes Become, then the resistance of distribution can change and the problem of there may be making signal transmission speed change when TFT drives, because This preferably minimizes lateral erosion variable quantity.Variable quantity is preferably smaller than 0.1 μm, shows the result in table 2 below
[table 2]
As described in above-mentioned table 2, in the case of using the etchant of embodiment 1~9, Cu etching speeds, cone Angle excellent, does not produce interface portion erosion and residue, the lateral erosion variable quantity evaluation result based on processing substrate number are also excellent It is different.
In addition, can be confirmed by Fig. 1, in the case of the copper system metal film etched by the etchant of embodiment 1, erosion Carve profile (profile) and rectilinear propagation is excellent, and residue is not observed.
On the other hand, in the case of using the etchant of comparative example 1~8, etching characteristic is bad.
In the case of comparative example 1 of the content of hydrogen peroxide less than Optimum Contents, Cu etching speeds are excessively slow and nothing occur The phenomenon of method etching, is 1 in the weight ratio of phosphate and sulfate:In the case of 2 comparative example 2, there are etching speed it is excessively slow, The problem of cone angle is big.It is 1 in weight ratio:In the case of 25 comparative example 3, the too fast and unmanageable process of etching speed is confirmed
It in the case where using ammonium sulfate as the comparative example 4 of sulfate, can be confirmed by Fig. 2, produce interface portion and corrode.This Outside, phosphite (- PO is being used3 3-) replace phosphate (- PO4 3-) comparative example 6 in the case of, can be confirmed by Fig. 3, produce it is residual Slag, the lateral erosion variable quantity (S/E) based on processing substrate number are very big.
In the case of comparative example 7 of the content of sulfate less than Optimum Contents, it is excessively slow to confirm Cu etching speeds, cone angle Greatly, the lateral erosion variable quantity based on processing number is big., can in the case where the content of sulfate exceedes the comparative example 8 of Optimum Contents The too fast and unmanageable process of etching speed is confirmed, the lateral erosion variable quantity (S/E) based on processing substrate number is very big.

Claims (12)

  1. A kind of 1. etchant of metal film, it is characterised in that relative to composition total weight, comprising：
    5~25 weight % of hydrogen peroxide,
    0.01~1 weight % of fluorine compounds,
    0.1~5 weight % of azole compounds,
    Water soluble compound 0.1~5 weight % of one intramolecular with nitrogen-atoms and carboxyl,
    0.001~5 weight % of phosphate comprising alkali or alkaline earth metal,
    0.01~5 weight % of EPE polyol EPE,
    0.1~5 weight % of sulfate comprising alkali or alkaline earth metal and
    The water of surplus,
    The weight ratio of the phosphate and sulfate is 1:3~1:20.
  2. 2. the etchant of metal film according to claim 1, the fluorine compounds are selected from by HF, NaF, NH4F、 NH4BF4、NH4FHF、KF、KHF2、AlF3And HBF4One or more of group of composition.
  3. 3. the etchant of metal film according to claim 1, it is characterised in that the azole compounds be selected from Three azole compounds, Aminotetrazole based compound, imidazole compound, indoles based compound, purine based compound, pyrazoles system In compound, pyridine based compound, pyrimidine compound, pyrroles's based compound, pyrrolidines based compound and pyrrolin based compound More than one.
  4. 4. the etchant of metal film according to claim 1, it is characterised in that one intramolecular has nitrogen The water soluble compound of atom and carboxyl is selected from alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, ammonia three One or more of acetic acid and methyl amimoacetic acid.
  5. 5. the etchant of metal film according to claim 1, it is characterised in that described to include alkali metal or alkaline earth The phosphate of metal is selected from one or more of sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate and dipotassium hydrogen phosphate.
  6. 6. the etchant of metal film according to claim 1, it is characterised in that the polyol type surface-active Agent is selected from one or more of glycerine, ethylene glycol, diethylene glycol, triethylene glycol and polyethylene glycol.
  7. 7. the etchant of metal film according to claim 1, it is characterised in that described to include alkali metal or alkaline earth The sulfate of metal is selected from one or more of sodium sulphate, potassium sulfate, niter cake and potassium acid sulfate.
  8. 8. the etchant of metal film according to claim 1, it is characterised in that the metal film is copper system metal Film.
  9. 9. the etchant of metal film according to claim 8, the copper system metal film is copper or the list of copper alloy Tunic or be multilayer film, the multilayer film is included in the group being made of molybdenum film, molybdenum alloy film, titanium film and titanium alloy film More than one film and film selected from one or more of copper film and tin-copper alloy film.
  10. A kind of 10. manufacture method of array substrate for display device, it is characterised in that including：
    A) on substrate formed gate wirings the step of,
    B) on the substrate comprising the gate wirings formed gate insulator the step of,
    C) on the gate insulator formed semiconductor layer the step of,
    D) on the semiconductor layer formed source electrode and drain electrode the step of and
    E) the step of forming the pixel electrode being connected with the drain electrode,
    A) the step or d) at least one step in step are included on the substrate the step of being laminated metal layer and make The step of being etched with etchant,
    The etchant is included relative to composition total weight：5~25 weight % of hydrogen peroxide, fluorine compounds 0.01~ 1 weight %, 0.1~5 weight % of azole compounds, an intramolecular have the water soluble compound 0.1~5 of nitrogen-atoms and carboxyl Weight %, 0.001~5 weight % of phosphate, 0.01~5 weight of EPE polyol EPE comprising alkali or alkaline earth metal The water of %, 0.1~5 weight % of sulfate comprising alkali or alkaline earth metal and surplus is measured,
    The weight ratio of the phosphate and sulfate is 1:3~1:20.
  11. 11. the manufacture method of array substrate for display device according to claim 10, it is characterised in that the display dress It is thin film transistor (TFT) (TFT) array base palte to put with array base palte.
  12. 12. a kind of array substrate for display device, it includes the etching solution combination any one of usage right requirement 1~9 Thing etches one or more of the gate wirings formed, source electrode and drain electrode.
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CN111172542A (en) * 2018-11-12 2020-05-19 东友精细化工有限公司 Silver thin film etching solution composition, etching method and metal pattern forming method
CN111187625A (en) * 2018-11-14 2020-05-22 三星显示有限公司 Etching composition, method of forming pattern, and method of manufacturing display device
CN111893488A (en) * 2020-08-04 2020-11-06 深圳市乾行达科技有限公司 Etching solution and preparation method thereof
CN112342547A (en) * 2019-08-07 2021-02-09 易安爱富科技有限公司 Etching liquid composition
CN113604804A (en) * 2021-07-07 2021-11-05 湖北兴福电子材料有限公司 Etching solution for stabilizing line width loss and etching cone angle in panel copper plating process
CN114075669A (en) * 2020-08-10 2022-02-22 东友精细化工有限公司 Etchant composition, method for forming wiring, and method for manufacturing array substrate for liquid crystal display device
WO2022047854A1 (en) * 2020-09-02 2022-03-10 Tcl华星光电技术有限公司 Etching solution composition for etching molybdenum/copper/molybdenum or molybdenum alloy/copper/molybdenum alloy three-layer metal wiring structure and use thereof

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KR20160112470A (en) * 2015-03-19 2016-09-28 동우 화인켐 주식회사 Etchant composition and manufacturing method of an array for liquid crystal display

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KR20160112470A (en) * 2015-03-19 2016-09-28 동우 화인켐 주식회사 Etchant composition and manufacturing method of an array for liquid crystal display

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CN111172542A (en) * 2018-11-12 2020-05-19 东友精细化工有限公司 Silver thin film etching solution composition, etching method and metal pattern forming method
CN111187625A (en) * 2018-11-14 2020-05-22 三星显示有限公司 Etching composition, method of forming pattern, and method of manufacturing display device
CN111187625B (en) * 2018-11-14 2022-08-19 三星显示有限公司 Etching composition, method of forming pattern, and method of manufacturing display device
CN112342547A (en) * 2019-08-07 2021-02-09 易安爱富科技有限公司 Etching liquid composition
CN112342547B (en) * 2019-08-07 2024-04-16 易安爱富科技有限公司 Etching liquid composition
CN111893488A (en) * 2020-08-04 2020-11-06 深圳市乾行达科技有限公司 Etching solution and preparation method thereof
CN114075669A (en) * 2020-08-10 2022-02-22 东友精细化工有限公司 Etchant composition, method for forming wiring, and method for manufacturing array substrate for liquid crystal display device
WO2022047854A1 (en) * 2020-09-02 2022-03-10 Tcl华星光电技术有限公司 Etching solution composition for etching molybdenum/copper/molybdenum or molybdenum alloy/copper/molybdenum alloy three-layer metal wiring structure and use thereof
CN113604804A (en) * 2021-07-07 2021-11-05 湖北兴福电子材料有限公司 Etching solution for stabilizing line width loss and etching cone angle in panel copper plating process
CN113604804B (en) * 2021-07-07 2022-09-23 湖北兴福电子材料股份有限公司 Etching solution for stabilizing line width loss and etching cone angle in panel copper plating process

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