CN107988598B - The manufacturing method of etchant and array substrate for display device - Google Patents

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

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Publication number
CN107988598B
CN107988598B CN201711262782.6A CN201711262782A CN107988598B CN 107988598 B CN107988598 B CN 107988598B CN 201711262782 A CN201711262782 A CN 201711262782A CN 107988598 B CN107988598 B CN 107988598B
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weight
film
etchant
phosphate
sulfate
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CN107988598A (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 manufacturing method of array substrate for display device and array substrate for display device, more specifically, it provides when manufacturing array substrate for display device, metal film can be etched together, the etchant of metal film, the manufacturing 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 with etching speed, cone angle excellent and etching multilayer film.The etchant of the metal film is characterized in that, relative to composition total weight, include: 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, sulfate 0.1~5 weight % and surplus comprising alkali or alkaline earth metal, and the weight ratio of phosphate and sulfate is 1:3~1:20.

Description

The manufacturing method of etchant and array substrate for display device
Technical field
The present invention relates to the manufacturing methods of etchant and array substrate for display device.
Background technique
In semiconductor device, in the step of process for forming metal wiring on substrate is generally included using following process: benefit With the metal film formation process of sputtering etc.；It is coated with using photoresist, is in the selective area of exposure and imaging photic anti- Lose agent formation process；And etching work procedure, and including the cleaning process etc. before and after Individual cells process.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 etching.
In such semiconductor device, it is primarily upon the resistance of metal wiring in recent years.This is because resistance is to induce RC The principal element of signal delay, especially in Thin Film Transistor-LCD (thin film transistor-liquid Crystal display, TFT-LCD) in the case where, panel size increases and high-resolution realization is increasingly becoming technological development Key.Therefore, in order in realizing the enlargement of the display device including TFT-LCD etc. necessary RC signal delay subtract It is few, it is necessary to develop low resistance substance.Therefore, actual conditions are to lead chromium to be used (Cr, resistivity: 12.7 × 10 in the past-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 used in the display devices such as type TFT-LCD and data wiring etc..
In this context, as new low resistive metal film, the copper systems metal film such as copper film and copper-molybdenum film is paid high attention to And its etchant, and research is actively being implemented to this.For example, in KR published patent the 2010-0090538th Disclosing has nitrogen-atoms comprising hydrogen peroxide, organic acid, phosphate compounds, water-soluble cyclic amine compound, an intramolecular With the etching solution group of the copper system metal film of the water soluble compound of carboxyl, fluorochemical, EPE polyol EPE and water Close object.However, being deposited in terms of the cone angle maintenance for handling number ongoing change in etching of thick film metal layer for above-mentioned etching solution Limiting to, interface portion leads to the problem of erosion when having etching multilayer film.
Existing technical literature
Patent document
Patent document 1: KR published patent the 2010-0090538th
Summary of the invention
Project to be solved
The object of the present invention is 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 generate the etchant of the metal film of residue.
The method to solve the problem
To achieve the goals above, the present invention provides a kind of etchant of metal film, which is characterized in that relative to Composition total weight includes: 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 The water of sulfate 0.1~5 the weight % and surplus of category,
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 Stating multilayer film includes film, Yi Jixuan selected from one or more of the group being made of molybdenum film, molybdenum alloy film, titanium film and titanium alloy film From the film of one or more of copper film and tin-copper alloy film.
In addition, the present invention provides a kind of manufacturing method of array substrate for display device characterized by comprising a) exist On substrate formed gate wirings the step of, b) on the substrate for including above-mentioned gate wirings formed gate insulating layer the step of, c) The step of formation source electrode and drain electrode in the step of forming semiconductor layer on above-mentioned gate insulating layer, d) on above-mentioned semiconductor layer Suddenly the step of and e) forming the pixel electrode connecting with above-mentioned drain electrode,
Above-mentioned a) step or d) at least one step in step include the steps that on aforesaid substrate be laminated metal layer, with And the step of being etched using etchant,
Above-mentioned etchant includes 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 groups for using above-mentioned metal film Close one or more of gate wirings, source electrode and drain electrode made of object etching.
Invention effect
Etchant of the invention is capable of providing following effect:, can when manufacturing array substrate for display device Interface when metal film being etched, cone angle, the lateral erosion variable quantity excellent with processing substrate number together, and etching multilayer film The etching outline in portion is excellent.
Detailed description of the invention
Fig. 1 be evaluation using embodiment 1 etchant etching Cu/MoNb duplicature after (a) etching section, (b) SEM photograph that etching outline and residue the presence or absence of generate.
Fig. 2 is invaded for generation interface portion after confirming the etchant etching Cu/MoNb duplicature using comparative example 4 The SEM photograph of erosion.
Fig. 3 is for generating residue after confirming the etchant etching Cu/MoNb duplicature for utilizing comparative example 6 SEM photograph.
Specific embodiment
The display device of etchant the present invention relates to the etchant of metal film and using the metal film With the manufacturing method of array substrate.
The present inventor in order to provide have when etch metal film etching speed and cone angle it is excellent and etching multilayer There is no interface portion to corrode when film and during the etchant of the excellent effect of etching outline is furtherd investigate, confirmation 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 where phosphate and sulfate, there can be said effect, 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, which is characterized in that relative to composition total weight, packet 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 be realized excellent cone angle and The etching speed of metal film.
In the case where the weight ratio of the phosphate in terms of said reference and sulfate is less than 1:3, etching speed is insufficient and nothing Method realizes adequately etching, it is possible to create the problem of cone angle becomes larger, more than 1:20, etching speed is too fast and is not easy Control process, and cone angle is more than 55 ° and to generate etching outline bad.
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 monofilm and multilayer film including copper or copper alloy, and the multilayer film includes to close selected from copper film and copper The film of one or more of golden film and selected from one of group being made of molybdenum film, molybdenum alloy film, titanium film and titanium alloy film with On film.
In addition, the concept of above-mentioned so-called alloy film further includes nitride film or oxidation 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 comprising molybdenum layer and the layers of copper formed on above-mentioned molybdenum layer, on Copper/molybdenum alloy film is stated to mean comprising Mo alloy and the layers of copper formed on above-mentioned Mo alloy, copper alloy/molybdenum alloy film Mean that, comprising Mo alloy and the copper alloy layer formed on above-mentioned Mo alloy, above-mentioned copper/titanium film, which is meant, includes Titanium layer and the layers of copper formed on above-mentioned titanium layer.
Above-mentioned copper alloy layer refers to that the layer formed by the alloy of following metal and copper, the metal are selected from by such as aluminium (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), one or more of group of compositions such as hafnium (Hf), tantalum (Ta) and tungsten (W).
Above-mentioned Mo alloy refers to that the layer formed by the alloy of following metal and molybdenum, the metal are selected from by such as titanium (Ti), one or more of group of compositions such as niobium (Nb), tungsten (W), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd) and indium (In).
In particular, 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 together.
Hereinafter, the composition for the etchant that the present invention will be described in detail.
Hydrogen peroxide
Hydrogen peroxide (H included in etchant of the invention2O2) it is that the etching to copper system metal film generates shadow Loud main oxidant, above-mentioned copper system metal film may 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, content is 5~25 weight %, more Preferably 17~23 weight %.In the case where content is lower 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 are insufficient and the problem of cannot achieve sufficient etching.It on the other hand, is more than 25 in content In the case where weight %, etching speed integrally becomes faster, therefore, it is difficult to control process, based on the increased fever of copper ion in composition Stability may will be greatly reduced.
Fluorine compounds
Fluorine compounds included in etchant of the 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, playing 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 composition total weight of the invention, content is 0.01~1 weight Measure %, more preferably 0.05~0.2 weight %.It, may in the case where the content of above-mentioned fluorine compounds is lower than 0.01 weight % Generate the etch residue of metal film.On the other hand, in the case where content is more than 1 weight %, there are the changes of glass substrate etching rate Big disadvantage.
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 preferred concrete example of above-mentioned fluorine compounds, can enumerate HF、NaF、NH4F、NH4BF4、NH4FHF、KF、KHF2、AlF3And HBF4Deng, it is preferable to use being selected from more than one such.
Azole compounds
The etching speed of the performance adjusting copper system metal film of azole compounds included in etchant of the invention, Reduce the CD loss (CD Loss) of pattern and improves the effect of the surplus in process.
Above-mentioned azole compounds are characterized in that, relative to composition total weight, content is 0.1~5 weight %, more excellent It is selected as 0.3~0.8 weight %.In the case where the content of the azole compounds in terms of said reference is lower 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, more than 5 weight %, copper film Excessively slow and molybdenum alloy film the etching speed of the etching speed of equal metal films is relatively excessively slow, thus the loss of activity time occurs, residual A possibility that staying the residue of molybdenum alloy increase.
Above-mentioned azole compounds are not particularly limited as long as azole compounds usually used in this field, but can be with The more preferably azole compounds of carbon atom number 1~30.More preferably it can be used 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 included in etchant of the invention has the water-soluble chemical combination of nitrogen-atoms and carboxyl Object prevents the selfdecomposition for the hydrogen peroxide that may occur when keeping etchant, and is etched to a large amount of substrate When prevent etching characteristic from changing.In general, using hydrogen peroxide etchant in the case where, keeping when by In hydrogen peroxide generation selfdecomposition, its storage time is not grown, and also has the risk factor there is a possibility that container explosion.But it is 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 is reduced Nearly 10 times, thus it is advantageously ensured that storage time and stability.
In particular, when largely remaining copper ion in etchant, may relatively mostly occur shape in the case where layers of copper The case where being no longer etched after oxidizing blackening at passivation (passivation) film, but in the case where adding above compound, It can prevent this phenomenon.
There is said one intramolecular the water soluble compound of nitrogen-atoms and carboxyl to be characterized in that, relative to of the invention Composition total weight, 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 lower than 0.1 weight %, a large amount of substrate (about 500) are etched After will 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 become smaller.
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 sarcosine (sarcosine) etc. it, can be used more than one such.
Phosphate comprising alkali or alkaline earth metal
Phosphate (- PO included in etchant of the invention4 3-) play cone angle profile and the etching for making pattern The good effect of profile.
Above-mentioned the phosphate (- PO comprising alkali or alkaline earth metal4 3-) it is one or two of phosphoric acid hydrogen by alkali metal Or phosphate made of alkaline-earth metal displacement can enumerate sodium dihydrogen phosphate (sodium phosphate as concrete example Monobasic), potassium dihydrogen phosphate (potassium phosphate monobasic), disodium hydrogen phosphate (sodium Phosphate dibasic) and dipotassium hydrogen phosphate (potassium phosphate dibasic) etc., it can be used selected from it One or more of.
It is above-mentioned it is phosphatic be characterized in that, relative to composition total weight of the invention, content is 0.001~5 weight Measure %, more preferably 0.05~0.3 weight %.The case where content phosphatic in terms of said reference is lower than 0.001 weight % 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
EPE polyol EPE included in etchant of the invention performance 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 The copper ion etc. dissolved out in etching solution inhibits the decomposition reaction of hydrogen peroxide to inhibit the activity of copper ion.If dropped in this way The activity of low copper ion then can steadily carry out process during using etching solution.
Above-mentioned EPE polyol EPE is characterized in that, relative to composition total weight of the invention, content is 0.01~5 weight %, more preferably 2.0~5.0 weight %.It is lower than 0.01 weight in the content of above-mentioned EPE polyol EPE In the case where 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 generating a large amount of foams.
Above-mentioned EPE polyol EPE can it is preferable to use be selected from glycerol (glycerol), ethylene glycol (ethylene Glycol), diethylene glycol (diethylene glycol), triethylene glycol (triethylene glycol) and polyethylene glycol One or more of (polyethylene glycol) etc., but it is not limited to this.
Sulfate comprising alkali or alkaline earth metal
Sulfate included in etchant of the invention plays the good effect of cone angle profile for making pattern, and Play the effect for adjusting the etching speeds of metal films such as copper film.
The above-mentioned sulfate comprising alkali or alkaline earth metal is one or two of sulfuric acid hydrogen by alkali metal or alkaline earth Sulfate made of metal replacement can be used as concrete example selected from sodium sulphate (sodium sulfate), potassium sulfate (potassium sulfate), sodium bisulfate (sodium hydrogensulfate) and potassium acid sulfate (potassium One or more of hydrogensulfate) etc., but it is not limited to this.
Above-mentioned sulfate is characterized in that, relative to composition total weight of the invention, 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 lower than 0.1 weight %, metal film Etch capabilities are insufficient and may cannot achieve sufficient etching, and are possible to generate and handle the bad equal etching characteristics of number evaluation not It is good.On the other hand, in the case where the content of above-mentioned sulfate is more than 5 weight %, because of the too fast and uncontrollable work of etching speed Sequence can not carry out stable process.
Water
The content of water included in etchant of the invention is that composition total weight is made to become 100 weight % Surplus.Above-mentioned water is not particularly limited, it is preferable to use deionized water.In addition, more preferably removing degree using embodiment water intermediate ion Water resistivity value be 18M Ω cm or more deionized water.
In addition, etchant of the invention can further include common additive in addition to the above ingredients. As above-mentioned additive, sequestering agent, anticorrosive etc. can be enumerated, but it is not limited to this, in order to make effect of the 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 be precipitated, therefore not preferably.
Ingredient included in etchant of the invention preferably has the purity for semiconductor process.
In addition, providing a kind of method for forming wiring as one embodiment of the invention comprising:
1) the step of forming molybdenum alloy film on substrate；
2) the step of forming copper system metal film on above-mentioned molybdenum alloy film；
3) the step of selectively leaving light reaction substance on above-mentioned copper system metal film；And
4) the step of above-mentioned copper system metal film and molybdenum alloy film being etched together using etchant of the invention.
Above-mentioned light reaction substance is preferably common photoresist, can be selected by common exposure and imaging process Leave to selecting property.
In addition, the present invention provides a kind of manufacturing method of array substrate for display device characterized by comprising
A) on substrate formed gate wirings the step of,
B) on the substrate for including above-mentioned gate wirings formed gate insulating layer the step of,
C) on above-mentioned gate insulating layer 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 connecting with above-mentioned drain electrode,
Above-mentioned a) step or d) at least one step in step include the steps that on aforesaid substrate be laminated metal layer, with And the step of being etched using etchant,
Above-mentioned etchant includes 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 %, sulfate 0.1~5 weight % and surplus comprising alkali or alkaline earth metal,
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., and but it is not limited to this, etching solution group of the invention Object is closed since residue will not be generated in etching, there is no the bad problems of electric short circuit or wiring, can realize 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 substrate.
In addition, etchant of the invention can etch together gate wirings, source electrode and drain electrode, the present invention It provides comprising one of gate wirings, source electrode and drain electrode made of the etchant etching using above-mentioned metal film Above array substrate for display device.
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 for illustrating the present invention, therefore the present invention is not limited by 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 Examples 1 to 9 and comparative example
By following compositions recorded in table 1 and content (weight %), etchant 180kg is manufactured.
[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)
The etching characteristic of<experimental example>etchant is evaluated
The etchant for using Examples 1 to 9 and comparative example 1~8 respectively, implements etching work procedure.Utilize injecting type The experimental facilities (model name: ETCHER (TFT), SEMES company) of etching mode, the temperature of etchant in etching work procedure It is set as 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 following table 2.
Test piece used in etching work procedure (Cu/MoNb) has used following test piece: at glass substrate (Ⅹ 100mm of 100mm) Upper vapor deposition 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 scheduled pattern.
The evaluation of 1. etching speed of experimental example
Naked eyes measurement endpoint detecting (End Point Detection, EPD), obtain different time etching speed (E/R, Etch Rate), etching speed is only evaluated with longitudinal etching speed.If by the thickness of the metal film etched Divided by EPD, then (time) per second can be found out(thickness)Etching speed, evaluated by following benchmark, and will As a result it is shown in table 2.
<Cu etching speed evaluation criteria>
Zero: good
Х: poor (to be less thanOr it is more than)
Unetch: it can not etch
2. cone angle of experimental example (Taperangle, °) evaluation
Cone angle (Taper angle) refers to the gradient on the inclined-plane copper (Cu).Cone angle is excessive or too small, can steam in subsequent film Occur to be become by bad caused crackle (crack) phenomenon of Step Coverage (step coverage) or subsequent film vapor deposition when plating Difficulty, therefore it is critically important for maintaining suitable cone angle.In this evaluation, evaluated by following benchmark, and the results are shown in Table 2.
<cone angle evaluation criteria>
Zero: good (45~55 °)
Х: poor (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 110 seconds etching periods, takes out and cleaned with deionized water, Then it is dried using drying device, removes photoresist using photoresist stripping machine (PR stripper).Cleaning After drying, using scanning electron microscope (SEM, model name: SU-8010, Hitachi, Ltd manufacture), confirm copper film (Cu) and Whether the erosion of molybdenum-niobium film (MoNb) interface portion generates, and show the result in following table 2.
Nothing: erosion is not generated
Whether can not confirming: not be etched and can not confirm erosion
The evaluation of 4. residue of experimental example
It is put into above-mentioned sample to start to spray, if reaching 110 seconds etching periods, takes out and cleaned with deionized water, Then it is dried using drying device, removes photoresist using photoresist stripping machine (PR stripper).Cleaning After drying, using scanning electron microscope (SEM, model name: SU-8010, Hitachi, Ltd's manufacture), measurement molybdenum-niobium is not eclipsed The phenomenon that carving and leaving, i.e. residue are evaluated by following benchmark, and show the result in following table 2.
Nothing: residue is not generated
Whether can not confirming: not be etched and can not confirm that residue generates
Lateral erosion (Sideetch, S/E) variable quantity evaluation of the experimental example 5. based on processing substrate number
Measure lateral erosion (μm) variable quantity changed with Cu ion concentration (300~4,000ppm).Lateral erosion (Side etch, S/ E) refer to the distance between the side photoresist end measured after etching and lower metal end.If side etching quantity changes Become, then the resistance of wiring can change and 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 following table 2
[table 2]
As recorded in above-mentioned table 2, using the etchant of Examples 1 to 9, Cu etching speed, cone Angle excellent, does not generate 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 where the copper system metal film of the etchant etching by embodiment 1, erosion It carves profile (profile) and rectilinear propagation is excellent, and residue is not observed.
On the other hand, using the etchant of comparative example 1~8, etching characteristic is bad.
In the case where the content of hydrogen peroxide is lower than comparative example 1 of Optimum Contents, Cu etching speed is excessively slow and nothing occurs The phenomenon that method etches, in the case where the weight ratio of phosphate and sulfate is comparative example 2 of 1:2, that there are etching speeds is excessively slow, The big problem of cone angle.In the case where weight ratio is comparative example 3 of 1:25, the too fast and uncontrollable process of etching speed is confirmed
It in the case where using comparative example 4 of the ammonium sulfate as sulfate, can be confirmed by Fig. 2, generate interface portion and corrode.This Outside, phosphite (- PO is being used3 3-) replace phosphate (- PO4 3-) comparative example 6 in the case where, can be confirmed by Fig. 3, generate it is residual Slag, the lateral erosion variable quantity (S/E) based on processing substrate number are very big.
In the case where the content of sulfate is lower than comparative example 7 of Optimum Contents, it is excessively slow to confirm Cu etching speed, cone angle Greatly, the lateral erosion variable quantity based on processing number is big.It, can in the case where the content of sulfate is more than comparative example 8 of Optimum Contents The too fast and uncontrollable process of etching speed is confirmed, the lateral erosion variable quantity (S/E) based on processing substrate number is very big.

Claims (9)

1. a kind of etchant of metal film, which is characterized in that relative to composition total weight, include:
5~25 weight % of hydrogen peroxide,
0.01~1 weight % of fluorine compounds,
0.1~5 weight % of azole compounds,
One intramolecular have nitrogen-atoms and carboxyl 0.1~5 weight % of water soluble compound,
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,
And do not include tartaric acid,
The phosphate be selected from one or more of sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate and dipotassium hydrogen phosphate,
The sulfate be selected from one or more of sodium sulphate, potassium sulfate, sodium bisulfate and potassium acid sulfate,
The weight ratio of the phosphate and sulfate is 1:3~1:20.
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. the etchant of metal film according to claim 1, which is characterized in that the azole compounds be selected from Three azole compounds, Aminotetrazole based compound, imidazole compound, indoles based compound, purine based compound, pyrazoles system It closes in object, pyridine based compound, pyrimidine compound, pyrroles's based compound, pyrrolidines based compound and pyrrolin based compound More than one.
4. the etchant of metal film according to claim 1, which is characterized 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 sarcosine.
5. the etchant of metal film according to claim 1, which is characterized in that the polyol type surface-active Agent is selected from one or more of glycerol, ethylene glycol, diethylene glycol, triethylene glycol and polyethylene glycol.
6. the etchant of metal film according to claim 1, which is characterized in that the metal film is copper system metal Film.
7. the etchant of metal film according to claim 6, the copper system metal film is the list of copper or copper alloy Tunic or be multilayer film, the multilayer film include 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.
8. a kind of manufacturing method of array substrate for display device characterized by comprising
A) on substrate formed gate wirings the step of,
B) on the substrate for including the gate wirings formed gate insulating layer the step of,
The step of c) forming semiconductor layer on the gate insulating layer,
D) on the semiconductor layer formed source electrode and drain electrode the step of and
E) the step of forming the pixel electrode connecting with the drain electrode,
A) the step or d) at least one step in step include the steps that metal layer is laminated on the substrate and make The step of being etched with etchant,
The etchant includes 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 %, sulfate 0.1~5 weight % and surplus comprising alkali or alkaline earth metal are measured, and does not include tartaric acid,
The weight ratio of the phosphate and sulfate is 1:3~1:20.
9. the manufacturing method of array substrate for display device according to claim 8, which is characterized in that the display device It is thin film transistor (TFT) (TFT) array substrate with array substrate.
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