CN107267987A - Etchant - Google Patents
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- CN107267987A CN107267987A CN201710196022.3A CN201710196022A CN107267987A CN 107267987 A CN107267987 A CN 107267987A CN 201710196022 A CN201710196022 A CN 201710196022A CN 107267987 A CN107267987 A CN 107267987A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
-
- 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
-
- 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
-
- 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
- C23F1/38—Alkaline compositions for etching refractory metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The present invention provides etchant, the etchant includes one or more of persulfate, fluorine compounds, inorganic acid, cyclic amine compound, organic acid and acylate, sulfoacid compound, sulfamic acid and water, also, the etchant does not include Environmental Regulation material.
Description
Technical field
A kind of method that metal wiring is manufactured the present invention relates to etchant and using it, more specifically, is related to
A kind of etchant not comprising Environmental Regulation material and the method using its manufacture metal wiring.
Background technology
Stable image is realized for the large area with display panel, response speed is improved more important.In order to
Response speed is improved, the conductance of signal wire etc. is more important.
In order to improve conductance, metal wiring can be formed as to single layer structure or sandwich construction, in order to form this metal
Distribution is, it is necessary to etching solution.
The demand of the increase in demand of display panel of the etching solution used in manufacture with to(for) display panel also one
With increase.Necessity accordingly, with respect to more environmentally friendly and excellent economy etching solution gradually increases.
The content of the invention
Embodiment provides a kind of etchant not comprising Environmental Regulation material and manufactures metal wiring using it
Method.
The etchant of one embodiment of the invention includes persulfate, fluorine compounds, inorganic acid, ring-type amine compounds
One or more of thing, organic acid and acylate, sulfoacid compound, sulfamic acid and water.
Sulfoacid compound can be methanesulfonic acid (methane sulfonic acid).
Persulfate can be selected from by potassium peroxydisulfate (K2S2O8), sodium peroxydisulfate (Na2S2O8) and ammonium persulfate ((NH4)2S2O8) composition one or more of group.
Inorganic acid can be selected from one or more of group being made up of nitric acid, sulfuric acid, phosphoric acid and perchloric acid.
Fluorine compounds can be selected from by ammonium fluoride (ammonium fluoride), sodium fluoride (sodium
Fluoride), potassium fluoride (potassium fluoride), ammonium acid fluoride (ammonium bifluoride), sodium bifluoride
One or more of group of (sodium bifluoride) and potassium hydrogen fluoride (potassium bifluoride) composition.
Cyclic amine compound can be selected from by Aminotetrazole (aminotetrazole), imidazoles (imidazole), indoles
(indole), purine (purine), pyrazoles (pyrazole), pyridine (pyridine), pyrimidine (pyrimidine), pyrroles
(pyrrole), one or more of group of pyrrolidines (pyrrolidine) and pyrrolin (pyrroline) composition.
Organic acid can select one or more of group of free carboxylic acid, dicarboxylic acids, tricarboxylic acids or tetrabasic carboxylic acid composition.
The etchant of one embodiment of the invention can include 0.5 weight % to 20 weight % persulfate.
The etchant of one embodiment of the invention can include 0.01 weight % to 2.0 weight % fluorine compounds.
The etchant of one embodiment of the invention can include 1.0 weight % to 10 weight % inorganic acid.
The etchant of one embodiment of the invention can include 0.5 weight % to 5.0 weight % cyclic amine compound.
The etchant of one embodiment of the invention can include 0.1 weight % to 10.0 weight % organic acid and 0.1
Weight % to 10.0 weight % acylate.
The etchant of one embodiment of the invention can include 0.1 weight % to 3.0 weight % sulfoacid compound.
The etchant of one embodiment of the invention can include 0.1 weight % to 5.0 weight % sulfamic acid.
It is also safe in liquid waste processing according to embodiment, using the teaching of the invention it is possible to provide while one kind does not include Environmental Regulation material
Etchant.
Further, since the etchant of embodiment, its solubility is also certain in higher copper ion concentration,
And the change of lateral erosion value is also smaller, therefore, it is possible to the substrate number increase handled with same amount of etching solution.Therefore, it is possible to push away
The replacing period of slow etching solution, so that more economical.
In addition, in the case where being etched using the etchant of embodiment, by metal wiring institute can be reduced
It in the damage of the substrate of part, and can also reduce the peeling of photonasty pattern, therefore the system in metal wiring can be prevented
The product for being possible to produce during making is bad.
Brief description of the drawings
Fig. 1 to Fig. 5 is the sectional view of the manufacture method for the metal wiring for representing the present embodiment.
Fig. 6 is the top view of a TFT regions included in enlarged representation thin film transistor display panel.
Fig. 7 is the sectional view along Fig. 6 hatching cutting marked with VII-VII.
Fig. 8 is to shoot the dissolving compared corresponding to the etchant of comparative example and the etchant of embodiment 1
The photo of the result of degree.
Fig. 9 is to represent according to copper concentration to be become in the etchant of comparative example and the etchant of embodiment 1
The chart of the change of the lateral erosion value of change.
Figure 10 is to forming photonasty pattern on substrate and utilizing the etching with embodiment 1 and each composition of comparative example
Liquid composition peels off the photo that the degree of photonasty pattern is compared.
Description of reference numerals
110、210：Substrate 120：Metal level
120′：Metal wiring 122：The first metal layer
124：Second metal layer 122 '：First metallic wiring layer
124′：Second metallic wiring layer 130：Photosensitive material layer
132：The exposed portion of photosensitive material layer
134：Photonasty pattern 140：Mask
220：Gate line 222：Gate electrode
222a：First grid metal level 222b：Second grid metal level
230：Data wire 232：Source electrode
234：Drain electrode 239a, b：Ohmic contact layer
240：Semiconductor layer 250：Gate insulator
260：Diaphragm 262：Contact hole
270：Pixel electrode
Embodiment
Below, various embodiments of the present invention are described in detail referring to the drawings so that the technical field of the invention
Those of ordinary skill be readily able to implement.The present invention can be realized in a number of different manners, be not limited to illustrate herein
Embodiment.
In order to clearly demonstrate the present invention, eliminate the part unrelated with explanation, throughout the specification, to identical or
Similar structural element uses identical reference.
In addition, for convenience of explanation, any size and thickness for representing each structural element shown in figure, therefore the present invention
Not necessarily it is defined in the content of diagram.In the accompanying drawings in order to clearly show that each layer and region and enlarged representation thickness.Also,
The local layer of enlarged representation and the thickness in region for convenience of explanation in the accompanying drawings.
In addition, when refer to layer, film, region, plate etc. a part be located at another part " top " or " on " when, not only wrap
Situation of the part positioned at " surface " of another part is included, and is additionally included between them there are other parts.
In contrast to this, when certain part is located at " surface " of another part, represent do not have other parts in centre.In addition, position
In the part as benchmark " top " or " on " refer to be located above or below part as benchmark, and do not imply that must
Must along the direction side opposite with gravity be located at " top " or " on ".
In addition, throughout the specification, when mentioning certain part " comprising " structural element, unless there are opposite record,
This expression is not precluded from other structures key element, but can further comprise other structures key element.
In addition, throughout the specification, when mentioning " in vertical view ", refer to situation during object part viewed from above,
When mentioning " on section ", refer to the situation of the section from side door face after cutting perpendicularly object part.
Below, the etchant of embodiments of the invention is illustrated.
The etchant of the present embodiment is used to form metal wiring, can be by forming the metal level on substrate
A part be etched to form metal wiring.The metal level being etched using the etchant of the present embodiment can
To be by being laminated multiple film formed by copper film, tin-copper alloy film, titanium film and titanium alloy film or two or more in them.Make
For one, the etchant of the present embodiment is used to etch the duplex film comprising titanium film and the copper film being laminated on titanium film, but
It is not limited to this.
Relative to gross weight, the etchant of the present embodiment includes persulfate, fluorine compounds, inorganic acid, ring-type
One or more of amines, organic acid and acylate, sulfoacid compound, sulfamic acid and water.Hereinafter, with this reality of use
Apply the feelings that the etchant of example is etched to the metal film being made up of the lower film comprising titanium and the upper membrane comprising copper
On the basis of condition, each component of etchant is illustrated.
Persulfate plays the effect for etching metal film as primary oxidizers.Relative to the gross weight of etchant
Amount, the persulfate containing 0.5 weight % to 20 weight % the present embodiment.It is less than 0.5 weight % in the content of persulfate
In the case of, it can not realize sufficient etching because rate of etch declines.On the contrary, the content in persulfate is higher than 20 weight %'s
In the case of, etching degree is difficult to control to because etching speed is too fast, metal membrane-coating over etching is thus likely to result in
(overetching)。
The persulfate of the present embodiment may include potassium peroxydisulfate (K2S2O8), sodium peroxydisulfate (Na2S2O8) or ammonium persulfate
((NH4)2S2O8), or can be the mixture for including the two or more compounds in them.
Fluorine compounds are etched to the lower film as titanium film, remove the residue for being possible to produce by etching.Phase
For the gross weight of etchant, the fluorine compounds containing 0.01 weight % to 2.0 weight % the present embodiment.In fluorination
The content of compound is difficult to the etching of titanium in the case of being less than 0.01 weight %, be higher than 2.0 weights in the content of fluorine compounds
Increase the generation of the residue as caused by the etching of titanium in the case of amount %.In addition, the content in fluorine compounds is higher than 2.0 weight %
In the case of, titanium can not only be etched, but also etch into the substrate for being laminated with titanium.
As one, the fluorine compounds of the present embodiment may include ammonium fluoride (ammonium fluoride), sodium fluoride
(sodium fluoride), potassium fluoride (potassium fluoride), ammonium acid fluoride (ammonium bifluoride), fluorine
Change hydrogen sodium (sodium bifluoride) or potassium hydrogen fluoride (potassium bifluoride), and can include to be selected from
The mixture of two or more compounds in them.
The inorganic acid of the present embodiment plays the effect of cooxidant.Can be according to shared by the inorganic acid in etchant
Content control etching speed.Inorganic acid can be reacted with the copper ion in etchant, thus, it is possible to prevent copper
The increase of ion and the decline for also preventing rate of etch.
Relative to the gross weight of etchant, the inorganic acid containing 1 weight % to 10 weight % the present embodiment.
In the case that the content of inorganic acid is less than 1 weight %, sufficient etching speed is unable to reach because rate of etch declines, in inorganic acid
Content be higher than 10 weight % in the case of, it is possible to cracked in the light-sensitive surface used in the etching of metal film
(crack) or the stripping of light-sensitive surface is caused.In the case of cracking or peel off in light-sensitive surface, it is possible to cause positioned at photosensitive
The metal level being made up of titanium film or copper film of the bottom of film is etched excessively.
The inorganic acid of the present embodiment may include nitric acid, sulfuric acid, phosphoric acid and perchloric acid, or can also include to be selected from them
In two or more compounds mixture.
The cyclic amine compound of the present embodiment is preservative.Relative to the gross weight of etchant, contain 0.5 weight
% is measured to the cyclic amine compound of 5.0 weight % the present embodiment.It is less than 0.5 weight % feelings in the content of cyclic amine compound
Under condition, there is the danger of over etching because of the raising of the rate of etch of copper film, be higher than 5.0 weight % in the content of cyclic amine compound
In the case of, the etching of degree needed for being possible to realize because of the decline of the rate of etch of copper film.
As one, the cyclic amine compound of the present embodiment may include Aminotetrazole (aminotetrazole), imidazoles
(imidazole), indoles (indole), purine (purine), pyrazoles (pyrazole), pyridine (pyridine), pyrimidine
(pyrimidine), pyrroles (pyrrole), pyrrolidines (pyrrolidine) or pyrrolin (pyrroline) or bag
Mixture containing the two or more compounds in them.
The organic acid of the present embodiment improves etching speed with its content increase in etchant, and organic
Hydrochlorate reduces etching speed with its content increase in etchant.Particularly, the acylate of the present embodiment is made
Played a role for chelate, copper is adjusted by the copper ion formation complex compound in the etchant with the present embodiment
Etching speed.Therefore, it is possible to by with the organic acid in the etchant of appropriate Level tune the present embodiment and organic
The content of hydrochlorate adjusts etching speed.
Relative to the gross weight of etchant, the present embodiment respectively containing 0.1 weight % to 10 weight % has
Machine acid and acylate.That is, relative to the gross weight of etchant, this implementation containing 0.1 weight % to 10 weight %
The organic acid of example, and, relative to the gross weight of etchant, contain 0.1 weight % to 10 weights with organic acid independently
Measure the acylate of % the present embodiment.
In the case where the content of organic acid is less than 0.1 weight %, because etching speed declines and is wanted within the process time
The substrate number of processing is reduced.In addition, in the case where the content of organic acid is more than 10 weight %, having because etching speed is too fast
There may be the damage of the copper film as caused by over etching.
In the case where the content of acylate is less than 0.1 weight %, because having can not postponing the etching speed of etching solution
There may be being damaged as caused by over etching, in the case where the content of acylate is more than 10 weight %, because of etching speed
Cross slow and the etching to copper film can not be carried out within the common time.
The organic acid of the present embodiment may include carboxylic acid, dicarboxylic acids, tricarboxylic acids or tetrabasic carboxylic acid.Specifically, as one, this
The organic acid of embodiment may include acetic acid (acetic acid), butyric acid (butanoic acid), citric acid (citric
Acid), formic acid (formic acid), gluconic acid (gluconic acid), glycolic (glycolic acid), malonic acid
(malonic acid), oxalic acid (oxalic acid), valeric acid (pentanoic acid), sulfobenzoic acid (sulfobenzoic
Acid), sulfosuccinic acid (sulfosuccinic acid), salicylic acid (salicylic acid), sulfosalicylic acid
(sulfosalicylic acid), benzoic acid (benzoic acid), lactic acid (lactic acid), glyceric acid (glyceric
Acid), butanedioic acid (succinic acid), malic acid (malic acid), tartaric acid (tartaric acid), isocitric acid
(isocitric acid), acrylic acid (propenoic acid), iminodiacetic acid (imminodiacetic acid) or second
Ethylenediamine tetraacetic acid (EDTA) (ethylenediaminetetraacetic acid；EDTA) or two kinds in them are included
Compound above.
The acylate of the present embodiment may include sylvite, sodium salt or the ammonium salt of foregoing organic acid or comprising choosing
Two or more compounds from them.
The sulfoacid compound of the present embodiment can be methanesulfonic acid (methane sulfonic acid).The first of the present embodiment
Sulfonic acid plays the effect of the Copper treatment performance for the etchant for improving the present embodiment.In addition, methanesulfonic acid is responsible for the auxiliary of copper
Oxidant is acted on, and is not in the rheological parameters' change with time of composition itself, plays the effect for making decoction stable.
Relative to the gross weight of etchant, the first sulphur containing 0.1 weight % to 3.0 weight % the present embodiment
Acid.
In the case where the content of methanesulfonic acid is less than 0.1 weight % relative to the gross weight of etchant, because can not
Be smoothly performed the effect of cooxidant and reduce the performance of processing substrate number, methanesulfonic acid content relative to etching
In the case that the gross weight of liquid composition is more than 3.0 weight %, because etching speed is drastically accelerated, it is possible to because of over etching
Cause metal membrane damage.
The sulfamic acid (sulfamic acid) of the present embodiment is prevents the additive of rheological parameters' change with time, in liquid waste processing
Play the central role of heating control effect.Further, since sulfamic acid is excellent to the chelate effect of copper ion and in etching work
Suppress the side reaction as caused by the copper ion being dissolved in decoction during skill, therefore, it is possible to maintain to etch shape long-term and stably.
Relative to the gross weight of etchant, the sulfamic acid of the present embodiment contains 0.1 weight % to 5.0 weights
Measure %.
In the case where the content of sulfamic acid is less than 0.1 weight % relative to the gross weight of etchant, because of hair
Thermal control effect reduces and temperature rising is likely to result in when disposing waste liquid, and because sulfamic acid is imitated to the chelating of copper ion
The copper ion concentration more Gao Ze that fruit declines and existed in decoction shows the more increased tendency of taper in required etching shape.
In the case where the content of sulfamic acid is more than 5.0 weight % relative to the gross weight of etchant, due to etching speed
Drastically accelerate, it is possible to cause metal membrane damage because of over etching.
In addition, the etchant of the present embodiment can further include such as etching conditioning agent, surfactant, pH
The compositions such as conditioning agent.
In addition, the etchant of the present embodiment can include surplus by its gross weight in the way of 100 weight %
Water.Now, water can be deionized water (deionized water).
As indicated above, the etchant of the present embodiment be used to being formed the metal wiring that is formed on substrate and
There is provided, as one, used to form the metal wiring for the multiple membrane structure being made up of titanium or copper.It is this as one
Metal wiring can be the gate wirings of thin film transistor base plate.This will be described in detail in a later process.
The etchant of the present embodiment replaces the p-methyl benzenesulfonic acid (p-toluene as Environmental Regulation material
Sulfonic acid) it is used as using the non-hydrogen peroxide system metal film etchant comprising sulfamic acid and methanesulfonic acid
Generate heat controlling agent, thus it is more environmentally friendly, and ageing stability is improved, the ageing stability represents also tie up even if time passage
The degree of etching solution performance is held, the effect being improved with the effect as heating controlling agent.
In addition, the etchant of preceding description can be used to manufacture metal wiring 120 '.Hereinafter, referring to figs. 1 to
The method that Fig. 5 forms metal wiring to the etchant using the present embodiment is illustrated.
Fig. 1 to Fig. 5 is the sectional view of the manufacture method for the metal wiring for representing the present embodiment.
The manufacture method of the metal wiring 120 ' of the present embodiment comprises the following steps：Metal level is formed on substrate 110
120；And metal level 120 is etched.
Fig. 1 is to represent to be formed with substrate 110 including the first metal layer 122 and second metal layer according to the present embodiment
The figure of the situation of 124 metal level 120, Fig. 5 is to represent to lose metal level 120 using the etchant of the present embodiment
Carve and be formed with the figure of the situation of metal wiring 120 '.
As shown in figure 1, can perform the step of forming metal level 120 on substrate 110.Metal level 120 can be lamination copper
Film, tin-copper alloy film, titanium film and titanium alloy film or the multiple film more than two of which.On substrate 110
The top of the first metal layer 122 be provided with second metal layer 124.The first metal layer 122 can be titanium film, second metal layer 124
It can be formed by copper film.
Now, before the step of being etched metal level 120, it can further comprise forming Fig. 4 on metal level 120
The step of shown photonasty pattern 134.
Fig. 2 represents using mask 140 to make and mask 140 after forming photosensitive material layer 130 on metal level 120
The figure of the situation of the corresponding regional exposure in opening portion.Fig. 3 is to remove mask 140 after exposing and show photosensitive material layer 130
The figure of middle exposed portion 132.Fig. 4 is represented by removing the residue in addition to exposed portion 132 in photosensitive material layer 130
Part is come the figure of the situation that forms photonasty pattern 134.Fig. 5 is represented photonasty pattern 134 is as mask and utilization is foregoing
The etchant of explanation metal level 120 is etched formed by metal wiring 120 ' figure.
As shown in Fig. 2 the step of forming the photonasty pattern 134 of the present embodiment is by being formed on metal level 120
Photosensitive material layer 130 on configuration by photonasty pattern 134 configured openings mask 140 after, by exposure make with it is photosensitive
Property pattern 134 is corresponding zone-hardened to be carried out.Afterwards as shown in figure 4, when removing unhardened photosensitive material layer 130,
Remain the part after the hardening in photosensitive material layer 130 and form photonasty pattern 134.Photonasty pattern 134 is after
The effect of mask is played in the step of being etched to metal level 120.
Fig. 5 is the shape for representing that metal level is etched and formed using the etchant of the present embodiment metal wiring
The figure of condition.After photonasty pattern 134 is formed, the etchant pair for utilizing preceding description as shown in Figure 5 is performed
The step of metal level 120 is etched.Because the detailed content on etchant is identical with preceding description, therefore omit
Repeat specification.
The etchant of the present embodiment can make the metal level 120 between photonasty pattern 134 and substrate 110 slow
Ground is etched.Now, it is not to form the metal wiring 120 ' with the side vertical with the surface of substrate 110, but is formed such as Fig. 5 institutes
Show has the metal wiring 120 ' of inclined side like that.Now, by the surface of substrate 110 and the inclined side of metal wiring 120 '
Angle between face is referred to as " cone angle (taper angle, θ) ".
The metal wiring 120 ' of the present embodiment can be formed with about 30 ° to 60 ° of cone using etchant
Angle, is preferably formed to have 30 ° to 40 ° of cone angle.In the case where cone angle is less than 30 °, due to being connect with photonasty pattern 134
The top area of tactile metal wiring 120 ' is narrow and is likely to decrease electric conductivity.In addition, in the case where cone angle is more than 60 °,
Due to the too high step between photonasty pattern 134 and the other conductive patterns for being laminated to the top of metal wiring 120 ' afterwards
And be possible to crack in the conductive pattern or break caused by crackle.
The distance between the end of photonasty pattern 134 and the end of metal wiring 120 ' difference are defined as " lateral erosion value
(Side etch (S/E), w) ", the lateral erosion value produced in the both sides of metal wiring 120 ' is defined as " deviateing (Skew) value ".Cause
This, deviation value is defined as twice of lateral erosion value.
The lateral erosion value scope of the metal wiring 120 ' of the present embodiment can have about 0.5 μm to 1.5 μm of scope, therefore deviate
Value can have 1.0 μm to 3.0 μm of scope.In this regard, will be described in more detail in association with Fig. 9 later.
The metal wiring 120 ' of the present embodiment can be the gate wirings used in thin film transistor base plate, but not limit
Due to this.
Below, as one of method of metal wiring of manufacture preceding description, to the metal wiring including the present embodiment
Thin film transistor display panel illustrate.The structure of the thin film transistor display panel of the present embodiment is shown in Fig. 6 and Fig. 7.
Fig. 6 is the figure of a TFT regions included in enlarged representation thin film transistor display panel, and Fig. 7 is represented along Fig. 6
The figure of section that cuts of the hatching that is marked with VII-VII.
Reference picture 6, including a thin film transistor (TFT), the thin film transistor (TFT) include the gate electrode being connected with gate line 220
222nd, the source electrode 232 being connected with data wire 230, the drain electrode 234 and semiconductor layer 240 that are connected with pixel electrode 270.
Fig. 7 is the section cut along Fig. 6 hatching marked with VII-VII, represents the laminated relationship of each structure.As schemed
Shown in 7, gate electrode 222 is provided with over the substrate 210.Semiconductor layer 240 is provided with the gate electrode 222, is partly being led
Source electrode 232 and drain electrode 234 facing with each other centered on channel region is provided with body layer 240.
Respectively can between source electrode 232 and semiconductor layer 240 and between drain electrode 234 and semiconductor layer 240
Ohmic contact layer 239a, 239b are provided with, and this ohmic contact layer 239a, 239b can be omitted.
It is formed with the channel region of source electrode 232, drain electrode 234 and semiconductor layer 240 and covers their protection
Film 260, is formed with contact hole 262 in diaphragm 260.Drain electrode 234 can pass through contact hole 262 and pixel described later electricity
Pole 270 is electrically connected.Channel region can be relative with the part of semiconductor layer 240 between source electrode 232 and drain electrode 234
Should.
For the electric insulation between gate electrode 222 and semiconductor layer 240, gate electrode 222 and semiconductor layer 240 it
Between can be set have gate insulator 250.
The gate electrode 222 and gate line 220 of the present embodiment can be by being etched come shape to identical gate metal layer
Into.In order to be etched to gate metal layer, the etchant of the present embodiment of preceding description can be used.
Below, the method for the thin film transistor display panel to manufacturing the present embodiment is described in more detail.
The manufacture method of the thin film transistor display panel 200 of the present embodiment comprises the following steps：Form gate line 220；Shape
Into data wire 230；And form semiconductor layer 240.
The step of forming gate line 220 include the gate line 220 of gate electrode 222 to be formed on substrate, more specifically and
Speech, comprises the following steps：Gate metal layer is formed on substrate；And gate metal layer is etched.
The gate metal layer of the present embodiment and gate line 220 formed by being etched to gate metal layer can be by copper
Film, tin-copper alloy film, titanium film and titanium alloy film or the multiple film of the two or more laminations in them.It is used as one, this implementation
The etchant of example is used to form gate line 220 and gate electrode 222 by being etched gate metal layer, wherein
Gate metal layer is by forming titanium film as first grid metal level 222a and being formed as second grid metal level 222b after copper film
The duplex film being laminated through them is constituted, but is not limited to this.Second grid metal level 222b feelings are being formed by titanium film
Under condition, the first grid metal level 222a for the bottom for being deposited on second grid metal level 222b can be formed by copper film.By titanium film shape
Into first grid metal level 222a formed for protective substrate, as one, the inorganic layer formed by silica can be improved
Adhesion between copper film.
Because the etchant for being etched to gate metal layer is identical with the composition of preceding description, therefore
Omit repeat specification.
In addition, in the present embodiment on to the gate line 220 and gate electrode for forming thin film transistor display panel
The etchant that 222 gate metal layer is etched is illustrated, but is not limited to this.For forming this reality
The metal wiring of data wire 230, source electrode 232 and drain electrode 234 of the thin film transistor display panel of example is applied by comprising copper
Or in the case that the metal of titanium composition is constituted, can be etched using the etchant of the present embodiment.
Due to the etchant of the present embodiment used as heating controlling agent it is non-comprising sulfamic acid and methanesulfonic acid
Hydrogen peroxide system metal film etchant replaces the p-methyl benzenesulfonic acid as Environmental Regulation material, therefore can provide more ring
Protect, ageing stability is improved and as the etchant that is also improved of effect of heating controlling agent.Further, since
The solubility of decoction itself is likely to increase as well, therefore can prevent the accessory substance that is generated by the evaporation of decoction, using identical
Decoction when, moreover it is possible to increase processing substrate number.
In addition, in the case of the metal wiring being etched using the etchant of the present embodiment, with using
Compared as the situation of the p-methyl benzenesulfonic acid of Environmental Regulation material, cone angle can be played similar with lateral erosion value or be more improved
Effect.
Below, for the effect of the etchant of verifying the present embodiment, illustrate to analyze according to this reality by testing
The embodiment 1 and embodiment 2 applying the component of the etchant of example and manufacture and for comparing for the purpose of each embodiment and
The use of the etchant of p-methyl benzenesulfonic acid is the result of comparative example.
In order to verify the performance of the heating controlling agent as the etchant of the present embodiment, using with such as [table 1]
The etchant of the embodiment 1 of described content, embodiment 2 and comparative example is compared to waste liquid the degree of heat.
Embodiment 1, embodiment 2 and comparative example described in [table 1] jointly comprise persulfonic acid amine (Ammonium
PerSulfate, APS), amine fluoride (Ammonium Fluoride, AF), nitric acid (HNO3), 5- Aminotetrazoles (5-
AminoTetraZole, ATZ), acetic acid (Acetic Acid, AcOH) and ammonium acetate (Ammonium Acetate, A.A), implement
Example 1 and embodiment 2 include the sulfamic acid (Sulfamic Acid) and methanesulfonic acid (Methane of different content respectively
Sulfonic Acid), include p-methyl benzenesulfonic acid (p-Toluene Sulfonic Acid, p-TSA) as comparative example 1.Prepare
Such as each etchant of embodiment 1, embodiment 2 and comparative example 1 to 5, and maintain each decoctions in thermostat with 70 DEG C
3000ppm copper powder is added afterwards, then determines heating temp, and result is documented in [table 1] simultaneously.Do not representing other
In the case of unit, the numerical value unit described in [table 1] is " weight % ".
[table 1]
As described in [table 1], it is known that the highest heating temp of embodiment 1 and embodiment 2 and the phase of comparative example 1 to 5
Seemingly or compared with comparative example 1 to 5 reduce.Particularly, the feelings of methanesulfonic acid and sulfamic acid are included simultaneously as embodiment 1 and 2
Highest heating temp of the average value of the highest heating temp of condition than the comparative example 2 to 5 individually comprising methanesulfonic acid or sulfamic acid
Average value it is lower, and with including the phase of comparative example 1 as the p-methyl benzenesulfonic acid for being intended to exclude the material used in the present embodiment
Compare, also show similar or relatively low highest heating temp.Particularly, it can confirm in sulfamic acid as in Example 1
Highest heating temp reduces in the case that content is higher than embodiment 2.
Below, selection embodiments of the invention in because highest heating temp is relatively low and the more stable implementation of waste liquid the degree of heat
Example 1 and comparative example 1 comprising the p-methyl benzenesulfonic acid as the material to be excluded in the present embodiment carry out the experiment of performance comparision
As a result illustrate.
Fig. 8 is pair with the embodiment 1 as the relatively low embodiment of highest heating temp and comprising being intended to as in the present embodiment
The result that the solubility of the corresponding etchant of comparative example 1 of the p-methyl benzenesulfonic acid of the material of exclusion is compared is clapped
The photo taken the photograph.For the solubility of the etchant that compares the present embodiment, illustrated in Fig. 8 with above-mentioned [table 1]
Described in embodiment 1 and the corresponding component of comparative example 1 etchant in, respectively dissolve 2000ppm, 4000ppm,
The concentration of copper ion is determined after 6000ppm and 8000ppm copper powder to compare the result of solubility.
As shown in figure 8, in the case of example 1, the copper powder amount dissolved more increases, then the copper ionized by dissolving
The concentration of ion is also increased in proportion to, and shows solubility also close to 100% result.But, in the situation of comparative example 1
Under, it is known that when the copper powder amount dissolved is less, show close to copper powder amount after 100% solubility be 8000ppm when be in
Existing 89% copper ion concentration, solubility is strongly reduced.
It follows that compared with including the etching solution of p-methyl benzenesulfonic acid as the comparative example 1, including sulfamic acid and first
In the case of the embodiment 1 of sulfonic acid, though dissolved copper powder amount increase, also can with close to 100% degree maintain Gao Rong
Xie Du.
It has been observed that because the methanesulfonic acid included in the etchant of the present embodiment is responsible for the cooxidant of copper
Effect, is also not in the rheological parameters' change with time of composition itself, and performance makes the stabilized effect of decoction, therefore can improve Copper treatment
Energy.Equally, it has been observed that the copper dissolution degree of the sulfamic acid of the present embodiment is also excellent, so as to be carried out in the substrate for having copper to deposition
Increase is dissolved in the solubility of the copper ion in decoction during etching, further amounts of substrate can be entered using an etching solution filling
Row etching.
Because the etchant of the present embodiment is simultaneously comprising methanesulfonic acid and sulfamic acid, therefore can confirm such as embodiment
1 has higher copper dissolution degree like that compared with comparative example 1.
In the case of the etchant that the present embodiment is applied in actual process, the increase of the copper ion dissolved
It is relevant with being etched into places number or processing substrate number.In other words, it is known that with the substrate that etching is repeated and can handle
Number increase, even and if be repeated and etch for several times, high-dissolvability can be also maintained, so as to prevent because of still undissolved copper
Ion residues produce the bad possibility of such as short circuit on substrate.
Even if in addition, the copper powder amount increase dissolved, can also maintain high-dissolvability, therefore can also prevent the evaporation because of decoction
Caused by accessory substance generation so that with higher ageing stability.
Fig. 9 is the etching solution combination for representing the component with embodiment 1 and comparative example 1 described in [table 1] as described above
The chart of the deviation value changes changed with copper concentration of thing.
In actual manufacturing process, from the lateral erosion value or deviation value for departing from the etchant being initially provided of
10% lateral erosion value or the position of deviation value are risen, and are interrupted and further are changed using and with new etchant.
Therefore, even if the etchant with low uncertainty of copper concentration increase, lateral erosion value or deviation value, which can increase, can utilize unit quantity
Come the substrate number handled, it can be said that more economical.
As shown in figure 9, in the case of example 1, the change of deviation value under higher copper concentration compared with comparative example 1
Also it is small, and 10% scope that the change of deviation value belongs on the basis of initial deviation values untill copper concentration is 7000ppm
It is interior, therefore the predictable substrate number that can be handled compared with comparative example 1 with equal amount is more.Deviation value is generation in both sides
Lateral erosion value sum, is generally defined as twice of lateral erosion value, therefore also can come pre- according only to the comparison of deviation value as shown in Figure 9
Survey the result of lateral erosion value.It is associated with Fig. 9 and understand, it may be said that etchant ratio corresponding with embodiment 1 correspond to than
Etchant compared with example 1 is more economical.
[table 2] is to confirm substrate by the etchant of each component with embodiment 1 and comparative example 1
Etching degree, prepare respectively byIt is set to be combined in each etching solution after three samples that the glass substrate of thickness is constituted
The etching of same time is carried out in thing to determine the result of etched speed.Because the etching speed of substrate is more high, it is etched into
The degree of injury being applied between the departure date on substrate is deeper, therefore the bad possibility occurrence of subsequent product is also possible to improve.
[table 2]
As described in table 2, due in the case of etchant same as Example 1, the erosion of substrate
Carve speed lower than the etchant of the comparative example 1 under the same terms, therefore can confirm to substrate protection with more favourable
Effect.
Figure 10 is to forming photonasty pattern on substrate and utilizing each component with embodiment 1 and comparative example 1
Etchant peels off the photo that the degree of photonasty pattern is compared.As shown in Figure 10, it can confirm in comparative example 1
In the case of pass through 80 seconds or so when there's almost no remaining photonasty pattern.But confirm in the case of example 1 through
Cross part photonasty pattern after 90 seconds and start stripping, even if reaching 100 seconds, there is also further amounts of photosensitive compared with comparative example 1
Property pattern.
Because photonasty pattern plays the effect of mask during being etched, therefore feel because of etchant
Photosensitiveness pattern will not smoothly produce etching in the case of quickly being peeled off, it is possible to producing what metal wiring was etched excessively
It is bad.
More than, the various experiments carried out to the etchant of the etchant using embodiment 1 and comparative example
As a result analysis is compared.It has been observed that with including the p-methyl benzenesulfonic acid (p-toluene as Environmental Regulation material
Sulfonic acid) comparative example 1 compare, the etchant of the present embodiment comprising embodiment 1 has similar or more
Low waste liquid heating temp.Although accordingly, it is capable to providing a kind of also safe not comprising Environmental Regulation material but in liquid waste processing
Etchant.
Further, since the etchant of the present embodiment its solubility under high copper ion concentration it is also certain and
The change of lateral erosion value is also small, and the substrate number increase being etched therefore, it is possible to the etchant using unit quantity is simultaneously
Also the replacing period of etchant can be postponed, so that more economical.
In addition, according to the etchant of the present embodiment, the substrate damage as caused by etchant can be reduced,
And it can also reduce the peeling of photonasty pattern, so as to prevent the product for being possible to produce in manufacturing process bad.
More than, embodiments of the invention are described in detail, but protection scope of the present invention is not limited to this, profit
Various modifications and improvement side with those skilled in the art of the basic conception of the invention defined in claims described later
Formula falls within protection scope of the present invention.
Claims (14)
1. a kind of etchant, persulfate, fluorine compounds, inorganic acid, cyclic amine compound, organic acid and organic are included
One or more of hydrochlorate, sulfoacid compound, sulfamic acid and water.
2. etchant according to claim 1,
The sulfoacid compound is methanesulfonic acid.
3. etchant according to claim 1,
The persulfate is selected from one or more of group being made up of potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate.
4. etchant according to claim 1,
The inorganic acid is selected from one or more of group being made up of nitric acid, sulfuric acid, phosphoric acid and perchloric acid.
5. etchant according to claim 1,
The fluorine compounds are selected from being made up of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium acid fluoride, sodium bifluoride and potassium hydrogen fluoride
One or more of group.
6. etchant according to claim 1,
The cyclic amine compound is selected from by Aminotetrazole, imidazoles, indoles, purine, pyrazoles, pyridine, pyrimidine, pyrroles, pyrroles
One or more of group of alkane and pyrrolin composition.
7. etchant according to claim 1,
The organic acid is to select one or more of group of free carboxylic acid, dicarboxylic acids, tricarboxylic acids or tetrabasic carboxylic acid composition.
8. etchant according to claim 1,
Include 0.5 weight % to 20 weight % persulfate.
9. etchant according to claim 1,
Include 0.01 weight % to 2.0 weight % fluorine compounds.
10. etchant according to claim 1,
Include 1.0 weight % to 10 weight % inorganic acid.
11. etchant according to claim 1,
Include 0.5 weight % to 5.0 weight % cyclic amine compound.
12. etchant according to claim 1, comprising：
0.1 weight % to 10.0 weight % organic acid；And
0.1 weight % to 10.0 weight % acylate.
13. etchant according to claim 1,
Include 0.1 weight % to 3.0 weight % sulfoacid compound.
14. etchant according to claim 1, includes 0.1 weight % to 5.0 weight % sulfamic acid.
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| KR1020160039353A KR102384921B1 (en) | 2016-03-31 | 2016-03-31 | Echant composition and manufacturing method for metal wire |
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| CN111172541B (en) * | 2018-11-12 | 2022-06-21 | 东友精细化工有限公司 | Silver thin film etching solution composition, etching method and metal pattern forming method |
| KR102198608B1 (en) * | 2018-11-12 | 2021-01-05 | 동우 화인켐 주식회사 | Etchant composition for silver thin layer and etching method and method for fabrication metal pattern using the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008057367A1 (en) * | 2006-11-01 | 2008-05-15 | Microchem Corp. | Epoxy removal process for microformed elctroplated devices |
| CN102977889A (en) * | 2011-09-02 | 2013-03-20 | 东友精细化工有限公司 | Etching solution composition for metal oxide layer containing gallium |
| CN104451681A (en) * | 2013-09-25 | 2015-03-25 | 三星显示有限公司 | Etching solution composition and method for forming thin film transistor substrate using the same |
| CN104911593A (en) * | 2014-03-14 | 2015-09-16 | 东友精细化工有限公司 | Etchant composition for a metal layer comprising phosphorous acid |
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| KR101527117B1 (en) * | 2013-06-27 | 2015-06-09 | 삼성디스플레이 주식회사 | Etchant and manufacturing method of metal wiring and thin film transistor substrate using the same |
| KR102150523B1 (en) * | 2014-01-28 | 2020-09-01 | 동우 화인켐 주식회사 | Etching solution composition for copper layer and titanium layer and method of preparing array substrate for liquid crystal display using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008057367A1 (en) * | 2006-11-01 | 2008-05-15 | Microchem Corp. | Epoxy removal process for microformed elctroplated devices |
| CN102977889A (en) * | 2011-09-02 | 2013-03-20 | 东友精细化工有限公司 | Etching solution composition for metal oxide layer containing gallium |
| CN104451681A (en) * | 2013-09-25 | 2015-03-25 | 三星显示有限公司 | Etching solution composition and method for forming thin film transistor substrate using the same |
| CN104911593A (en) * | 2014-03-14 | 2015-09-16 | 东友精细化工有限公司 | Etchant composition for a metal layer comprising phosphorous acid |
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