CN104233299B - Etchant and engraving method - Google Patents
Etchant and engraving method Download PDFInfo
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- CN104233299B CN104233299B CN201410269845.0A CN201410269845A CN104233299B CN 104233299 B CN104233299 B CN 104233299B CN 201410269845 A CN201410269845 A CN 201410269845A CN 104233299 B CN104233299 B CN 104233299B
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
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- General Chemical & Material Sciences (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
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Abstract
The present invention relates to etchant and engraving method.[problem] is it is an object of the invention to provide etchant and uses its engraving method, in the etching together by the stacked film comprising titanium mesentery and copper system film, the fine rule of desired width is can obtain, in addition, can obtain the fine rule of preferable section shape.[solution] the present invention relates to a kind of etchant, it is used to together etch the stacked film comprising titanium mesentery and copper system film, it is characterised in that including the aqueous solution, the aqueous solution contains：(A) hydrogen peroxide：0.1~15 mass %；(B) fluorine ion supply source：0.02~2 mass %；(C) organic carboxyl acid：5~60 mass %；(D) has at least one kind of compound in the compound of 6 circle heterocycles containing more than 1 nitrogen-atoms and containing 3 double bonds selected from azole compounds and in the structure：0.01~5 mass %.
Description
Technical field
A kind of engraving method the present invention relates to etchant and using the etchant, in more detail, is related to
And it is a kind of be used for by the stacked film comprising titanium mesentery and copper system film together etching solution compound for etching and use the etching solution group
The engraving method of compound.
Background technology
Known with flat-panel monitor etc. is the wiring material of the display of representative to meet the maximization of display and height
Resolution ratioization is such to be required, uses copper or the distribution using copper as principal component, and and the titanium to titanium or titanium nitride etc. for representative
It is metal as barrier film.It is known to have a variety of Wet-type etching technologies on copper and the multilayer film of titanium system.
For example, Patent Document 1 discloses a kind of plural layers etching solution comprising layers of copper and titanium layer, it contained
Hydrogen oxide, nitric acid, fluorine ion supply source, azoles, quaternary ammonium hydroxide and stabilizer of hydrogen peroxide, and l.5~2.5 pH is.In addition,
Patent Document 2 discloses a kind of etching solution, it is characterised in that contains fluorine ion supply source, hydrogen peroxide, sulfate, phosphorus
Hydrochlorate, azole compounds and solvent.
Prior art literature
Patent document
Patent document 1：WO2011-093445 publications
Patent document 2：Japanese Unexamined Patent Publication 2008-288575 publications
The content of the invention
The invention problem to be solved
However, for example, in order to by the way that the stacked film comprising titanium mesentery and copper system film is etched to be formed comprising titanium together
The fine rule of mesentery and copper system film and use etching solution disclosed above when, there are the following problems：Sometimes uncontrollable etching speed,
The fine rule of desired width can not be obtained, or the fine rule of desired section shape can not be obtained sometimes.The section shape of preferable fine rule
Shape is the shape that fine rule upper width is less than fine rule lower width, on the contrary, in the section shape of fine rule, when the width on fine rule top
When degree is more than or equal to the width of fine rule bottom, fine rule is easily damaged, and it is not preferable.When using conventional etching solution, in fine rule
Section shape in, mostly fine rule upper width be more than or equal to fine rule lower width shape.
Therefore, the etching it is an object of the present invention to provide a kind of etchant and using the etchant
Method, it can obtain the fine rule of desired width, Er Qieke in the etching in the lump to the stacked film comprising titanium mesentery and copper system film
Obtain the fine rule of preferable section shape.
The means to solve the problem
The present inventor etc. have made intensive studies to solve above-mentioned problem, are as a result found that a kind of etchant energy
Solve above-mentioned problem, so far complete the present invention, the etchant is characterised by, including the aqueous solution, described water-soluble
Liquid contains (A) hydrogen peroxide, (B) fluorine ion supply source, (C) organic carboxyl acid and (D) and is selected from azole compounds and has in the structure
There is at least one kind of compound in the compound of 6 circle heterocycles containing more than 1 nitrogen-atoms and containing 3 double bonds.
That is, the present invention provides a kind of etchant, and it is used for the stacked film comprising titanium mesentery and copper system film together
Etching, it is characterised in that including the aqueous solution, the aqueous solution contains：(A) hydrogen peroxide：0.1~15 mass %；(B) fluorine from
Sub- supply source：0.02~2 mass %；(C) organic carboxyl acid：5~60 mass %；(D) is selected from azole compounds and in the structure
At least one kind of compound in compound with 6 circle heterocycles containing more than 1 nitrogen-atoms and containing 3 double bonds：0.01~5 matter
Measure %.
In addition, the present invention provides a kind of engraving method for etching the stacked film comprising titanium mesentery and copper system film together, its
It is characterised by, uses above-mentioned etchant.
Invention effect
According to the present invention, for by the stacked film comprising titanium mesentery and copper system film together etching solution compound for etching
In, the fine rule of desired width is can obtain, in addition, in the section shape of fine rule, can obtain fine rule upper width less than under fine rule
The fine rule of portion's width.A kind of etchant and the engraving method using the etchant can be provided.
Embodiment
Below, embodiments of the present invention are illustrated.
First, " the titanium mesentery " described in this specification is not particularly limited as long as film for titaniferous, will contain choosing
From Titanium and with Ti-Ni alloy etc. titanium mesentery is referred to as more than a kind of film in the titanium alloy of representative.
In addition, " copper system film " described in this specification is not particularly limited, such as will contain as long as film for cupric
Have selected from metallic copper and copper system film is referred to as more than a kind of film in the copper alloy of representative with corronil etc..
In the etchant of the present invention, the concentration of (A) hydrogen peroxide (following, to be sometimes referred to simply as (A) composition) is only
To be adjusted according to the desired thickness as the stacked film comprising titanium mesentery and copper system film for being etched material and/or width suitable
, but preferably 0.1~15 mass %, particularly preferably 0.5~10 mass % situation.When the concentration of (A) composition is less than 0.1
During quality %, sufficient etching speed can not be obtained, it is not preferable, on the other hand, when more than 15 mass %, is difficult to control sometimes
Etching speed processed, it is not preferable.
(B) fluorine ion supply source (following, to be sometimes referred to simply as (B) composition) used in the etchant of the present invention
As long as producing fluorine ion in etchant, it is not particularly limited, such as can enumerate：Hydrofluoric acid, ammonium fluoride, fluorination
Hydrogen ammonium, sodium fluoride, potassium fluoride, lithium fluoride etc..Here, for the fluoride salt of alkali metal, the alkali after etching process sometimes
Metal residual preferably uses hydrofluoric acid, ammonium fluoride, ammonium acid fluoride in etched basal body.
In the etchant of the present invention, (B) if composition concentration according to desired as being etched material
Thickness and/or the width suitable regulation of stacked film comprising titanium mesentery and copper system film, but preferably 0.02~2 mass %, it is special
Not preferably 0.05~1 mass %.When the concentration of (B) composition is less than 0.02 mass %, sufficient etching speed can not be obtained, therefore
Not preferably, on the other hand, when more than 2 mass %, etching glass is understood when etched basal body uses glass sometimes, thus it is unexcellent
Choosing.
In the etchant of the present invention, (C) organic carboxyl acid (following, to be sometimes referred to simply as (C) composition) is as long as be tool
There is the organic compound of carboxyl, be not particularly limited, such as can enumerate：Tetrabasic carboxylic acid, tricarboxylic acids, dicarboxylic acids, monocarboxylic acid and
Their acid anhydrides.
As above-mentioned tetrabasic carboxylic acid, the acid anhydride of tetrabasic carboxylic acid one or tetracarboxylic dianhydride, such as can enumerate：Compound (C- exemplified below
1)~(C-19) tetrabasic carboxylic acid, the acid anhydride or dianhydride for forming tetrabasic carboxylic acid dehydration.
[changing 1]
[changing 2]
[changing 3]
As above-mentioned tricarboxylic acids, the acid anhydride of tricarboxylic acids one, such as can enumerate：Compound (C-20)~(C-23) being exemplified below
Tricarboxylic acids, by the acid anhydride that forms of tricarboxylic acids dehydration.
[changing 4]
As above-mentioned dicarboxylic acids, such as can enumerate：Oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid and by these two
The acid anhydride that carboxylic acid dehydration forms.
As above-mentioned monocarboxylic acid, such as can enumerate：Acetic acid, formic acid, propionic acid etc..
In the etchant of the present invention, as preferable (C) composition, such as it can enumerate：Citric acid, butanedioic acid,
Glutaric acid, adipic acid, oxalic acid and acetic acid, in the case of using citric acid, the storage stability of etching solution is high, therefore especially excellent
Choosing.
In the etchant of the present invention, (C) if composition concentration according to desired as being etched material
Thickness and/or the width suitable regulation of stacked film comprising titanium mesentery and copper system film, are 5~60 mass %, preferably 10
~50 mass %.When the concentration of (C) composition is less than 5 mass %, etch capabilities occur when etching solution being used continuously for a long time
The situation of disappearance, it is not preferable, on the other hand, when the concentration of (C) composition is higher than 50 mass %, is difficult to control etching speed sometimes
Degree, it is not preferable.
(D) used in etchant to the present invention, which is selected from azole compounds and had in the structure, contains 1
In the compound of above nitrogen-atoms and 6 circle heterocycles containing 3 double bonds at least one kind of compound (it is following, sometimes referred to simply as (D) into
Point) illustrate.
Above-mentioned azole compounds are not particularly limited, as long as to have in the structure containing more than 1 nitrogen-atoms and containing 2 pairs
The compound of 5 circle heterocycles of key, such as can enumerate：Using 1- methylpyrroles as the azoles chemical combination such as alkyl pyrroles of representative and pyrroles
Thing；Using 1- methylimidazoles as the alkyl imidazole of representative, adenine, 1,3- imidazoles (below, sometimes referred to simply as imidazoles) and pyrazoles etc.
Diazole compounds；1,2,4- triazole, 5- methyl isophthalic acid H- BTAs and 1H- BTAs (following, sometimes referred to simply as benzo three
Azoles) and the triazole compounds such as 3- amino -1H- triazoles；1H-TETRAZOLE, 5- methyl isophthalic acid H- tetrazoliums, 5- phenyl -1H-TETRAZOLE and 5- ammonia
The tetrazole compounds such as base -1H-TETRAZOLE (below, sometimes referred to simply as 5- Aminotetrazoles)；1,3- thiazoles, 4- methylthiazols and isothiazole
Deng thiazolium compounds, isoxazole Deng oxazole compounds.Wherein, preferably adenine and tetrazole compound, wherein, particularly preferred gland is fast
Purine and 5- amino -1H-TETRAZOLE.As (D) composition, when using azole compounds, even in the minimum for forming fine rule
Spending more than the etching period needed will not also impact in the case of being etched to the quality of obtained fine rule, therefore excellent
Choosing.
The above-mentioned compound for having 6 circle heterocycles containing more than 1 nitrogen-atoms and containing 3 double bonds in the structure does not have special limit
It is fixed, as long as to have the compound of 6 circle heterocycles containing more than 1 nitrogen-atoms and containing 3 double bonds (below, to remember sometimes in the structure
For pyridine based compound), such as can enumerate：Using 2- picolines as the alkyl pyridinium compounds of representative, with 2- amino pyrroles
Pyridine and aminopyridine compounds, pyridine, pyrazine, pyrimidine, pyridazine, triazine and tetrazine that 2- (2- amino-ethyls) pyridine is representative,
It is preferred that aminopyridine compounds, wherein, particularly preferred PA.
In the etchant of the present invention, (D) if composition concentration according to desired as being etched material
Thickness, width and the desired narrow line shape of stacked film comprising titanium mesentery and copper system film are suitably adjusted, and are 0.01~5 matter
Measure %, preferably 0.05~0.5 mass %.When the concentration of (D) composition is less than 0.01 mass %, what is obtained after the etching is thin
In the section shape of line, the width on fine rule top is obtained sometimes more than or equal to the fine rule of the width of fine rule bottom, it is not preferable, separately
On the one hand, the raising of fiting effect is not found even if amount of the addition more than 5 mass % yet.(D) concentration of composition is being used alone
In the case of azole compounds or pyridine based compound, refer to the concentration of azole compounds or pyridine based compound, make in mixing
In the case of with azole compounds or pyridine based compound, refer to the concentration sum of azole compounds or pyridine based compound.Give
With explanation, the concentration rate of azole compounds or pyridine based compound when being used in mixed way azole compounds and pyridine based compound
Preferably 1：30~30：1 scope, more preferably 1：25~25：The situation of 1 scope, from the extra high angle of additive effect
Consider, particularly preferably 1：5~5：The situation of 1 scope.
In addition, the present invention etchant in, except above-mentioned (A) composition, (B) composition, (C) composition and (D) composition with
Outside, additive known to can also coordinating in the range of effect of the present invention is not hindered.As the additive, can enumerate：Etching
The stabilizer of liquid composition, the solvable agent of each composition, defoamer, pH adjusting agent, proportion conditioning agent, viscosity modifier, moistening
Property improver, chelating agent, oxidant, reducing agent, surfactant etc., 0.001 is generally using concentration during these additives
The mass % of quality %~50 scope.
Wherein, as pH adjusting agent, such as can enumerate：The inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid and its salt, water solubility are organic
The sour alkali hydroxide such as (in addition to the organic carboxyl acid of above-mentioned (C) composition) and its salt, lithium hydroxide, sodium hydroxide, potassium hydroxide gold
Belong to alkali hydroxide earth metal class, ammonium carbonate, lithium carbonate, sodium carbonate, the potassium carbonate such as class, calcium hydroxide, strontium hydroxide, barium hydroxide
Deng the quaternary ammonium hydroxide such as alkali carbonate class, TMAH, choline class, ethamine, diethylamine, triethylamine, hydroxyl
The organic amines such as ethamine, ammonia, they can use a kind or be mixed with two or more.When using pH adjusting agent, as long as addition
To reaching desired pH.It is explained, etchant of the invention is preferably in the range of pH1~5.If pH mistakes
Low, then the etching speed of copper becomes too fast, causes the refinement of copper wiring to become big.If pH not only makes hydrogen peroxide more than 5
Stability reduces, and Er Qietong, the dissolution velocity of particularly titanium become extremely slow, and etching needs the time, and it is not preferable,
In addition, as surfactant, anionic surfactant, cationic activating agent and both sexes table can be added
Face activating agent.As anionic surfactant, such as can enumerate：Polyoxyalkylene alkyl ether, polyoxy alkylidene alkene ether,
(the addition form of ethylene oxide and propylene oxide can be random shape, any of block-wise to polyoxyethylene polyoxy-propylene
Kind), polyethylene glycol propylene oxide adduct, polypropylene glycol ethylene oxide adduct, the oxirane and epoxy of Alkylenediamine
The random or block addition product of propane, fatty acid glyceride or its ethylene oxide adduct, sorbitan fatty acid ester, polyoxy
Ethene sorbitan fatty acid ester, Alkylpolyglucoside, fatty monoethanol amide or its ethylene oxide adduct, fat
Acid-N- methyl single ethanol amide or its ethylene oxide adduct, fatty diglycollic amide or its ethylene oxide adduct, sucrose
Fatty acid ester, alkyl (poly-) glycerin ether, polyglyceryl fatty acid ester, cithrol, fatty acid methyl ester ethoxylate,
N- chain alkyl diformazan amine oxides etc..Wherein, using Alkylenediamine oxirane and expoxy propane it is random or embedding
During section addition product, the linearity of obtained fine rule is good, and the storage stability of etching solution is good, therefore it is preferred that.In Alkylenediamine
Oxirane and expoxy propane random or block addition product in, it is low from foaming characteristic using in the case of trans-addition thing
From the point of view of, further preferably.As cationic surfactant, such as can enumerate：Alkyl (alkenyl) leptodactyline,
Dialkyl group (alkenyl) dimethyl ammonium, alkyl (alkenyl) quaternary ammonium salt, the list containing ether or ester group or amide groups or dialkyl group (alkene
Base) quaternary ammonium salt, alkyl (alkenyl) pyridiniujm, alkyl (alkenyl) dimethyl benzyl ammonium salt, alkyl (alkenyl) isoquinolin salt, two
Alkyl (alkenyl) alkylbenzyldimethylasaltsum saltsum, polyxyethylated (alkenyl) amine, alkyl (alkenyl) amine salt, polyamines derivative of fatty acid, amylalcohol
Derivative of fatty acid, benzalkonium chloride, benzethonium chloride etc..As amphoteric surfactant, such as can enumerate：Carboxybetaine, sulphur
Base glycine betaine, phosphonic acids glycine betaine, amidoamino acid, imidazolinium betaine system surfactant etc..Using during surfactant
Concentration is usually the mass % of 0.001 mass %~10 scope.
In the etchant of the present invention, the composition beyond mentioned component is water.Therefore, etching solution group of the invention
Compound is provided in the form of the aqueous solution of the mentioned component containing ormal weight.
The etchant of the present invention uses when for the stacked film comprising titanium mesentery and copper system film to be etched together.
Titanium mesentery both can be the stacked film of 1 layer or more than 2 layers.In addition, copper system film both can be 1 layer or 2 layers
Stacked film above.In the stacked film comprising titanium mesentery and copper system film, copper system film both can be the upper strata of titanium mesentery, can also
It is the lower floor of titanium mesentery, may be located on the upper and lower of titanium mesentery.In addition, in the stacked film comprising titanium mesentery and copper system film
In or titanium mesentery and the alternately laminated composition formed of copper system film.
It is used for etch the stacked film comprising titanium mesentery and copper system film together using etching agent composite of the invention
Engraving method is not particularly limited, and can be used well-known in general engraving method, can be enumerated：Utilize impregnated, spraying
The engraving method of formula, rotary etc..For example, the order on glass substrate according to titanium, copper is being laminated by atomizing etching method
Matrix be etched in the case of, by base material spray the present invention etchant, can lose on the glass substrate
Carve titanium film and copper film.
It is explained, etching condition now is not particularly limited, and can be appointed according to the shape of etch target and/or thickness etc.
Meaning setting.For example, spray condition is preferably 0.0lMpa~0.2Mpa, particularly preferably 0.01Mpa~0.1MPa.In addition, etching
Preferably 10 DEG C~50 DEG C, particularly preferred 20 DEG C~50 DEG C of temperature.The temperature of etchant rises because of reaction heat sometimes,
Therefore, if necessary, in order to maintain in the range of said temperature, temperature can also be controlled by known approaches.In addition, during etching
As long as it is the abundant necessary time that etch target can be fully etched between, therefore, is not particularly limited.If for example,
For the etch target of 100 μm or so of 1 μm or so of thickness, 10 μm or so of line width and opening portion, as long as then entering in said temperature scope
The row etching of 10~300 seconds or so.
The etchant of the present invention and the engraving method of use etchant can be mainly in processing liquid crystal displays
Suitably make when the electrode or distribution of device, plasma scope, touch panel, organic EL, solar cell, ligthing paraphernalia etc.
With.
Embodiment
Below, the present invention is explained by embodiment and comparative example, but the present invention is not limited to this.
[embodiment 1]
Etchant is prepared with the proportioning shown in table 1, obtains product No.1~22 of the present invention.It is explained, content
Surplus is water.
Table 1
| Product No. of the present invention | (A) composition (quality %) | (B) composition (quality %) | (C) composition (quality %) | (D) composition (quality %) |
| 1 | Hydrogen peroxide (1) | Ammonium acid fluoride (0.5) | Citric acid (20) | 5- Aminotetrazoles (0.1) |
| 2 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Citric acid (20) | 5- Aminotetrazoles (0.1) |
| 3 | Hydrogen peroxide (10) | Ammonium acid fluoride (0.5) | Citric acid (20) | 5- Aminotetrazoles (0.1) |
| 4 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.05) | Citric acid (20) | 5- Aminotetrazoles (0.1) |
| 5 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.2) | Citric acid (20) | 5- Aminotetrazoles (0.1) |
| 6 | Hydrogen peroxide (5) | Ammonium acid fluoride (1) | Citric acid (20) | 5- Aminotetrazoles (0.1) |
| 7 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Citric acid (20) | 5- Aminotetrazoles (0.01) |
| 8 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Citric acid (20) | 5- Aminotetrazoles (0.5) |
| 9 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Citric acid (10) | 5- Aminotetrazoles (0.1) |
| 10 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Citric acid (50) | 5- Aminotetrazoles (0.1) |
| 11 | Hydrogen peroxide (5) | Ammonium fluoride (0.5) | Citric acid (20) | 5- Aminotetrazoles (0.1) |
| 12 | Hydrogen peroxide (5) | Hydrofluoric acid (0.5) | Citric acid (20) | 5- Aminotetrazoles (0.1) |
| 13 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Citric acid (20) | BTA (0.1) |
| 14 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Citric acid (20) | Imidazoles (0.1) |
| 15 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Citric acid (20) | PA (0.1) |
| 16 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Citric acid (20) | Adenine (0.1) |
| 17 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Acetic acid (20) | 5- Aminotetrazoles (0.1) |
| 18 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Oxalic acid (20) | 5- Aminotetrazoles (0.1) |
| 19 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Malonic acid (20) | 5- Aminotetrazoles (0.1) |
| 20 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Butanedioic acid (20) | 5- Aminotetrazoles (0.1) |
| 21 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Glutaric acid (20) | 5- Aminotetrazoles (0.1) |
| 22 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Adipic acid (20) | 5- Aminotetrazoles (0.1) |
[Comparative examples A]
Etchant is prepared with the proportioning shown in table 2, obtains comparing product No.1~6.Be explained, content it is remaining
Measure as water.
Table 2
| Compare product No. | (A) composition (quality %) | (B) composition (quality %) | (C) composition (quality %) | (D) composition (quality %) |
| 1 | Nothing | Ammonium acid fluoride (0.5) | Citric acid (20) | 5- Aminotetrazoles (0.1) |
| 2 | Hydrogen peroxide (5) | Nothing | Citric acid (20) | 5- Aminotetrazoles (0.1) |
| 3 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Citric acid (20) | Nothing |
| 4 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Nothing | 5- Aminotetrazoles (0.1) |
| 5 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Sulfuric acid (20) | 5- Aminotetrazoles (0.1) |
| 6 | Hydrogen peroxide (5) | Ammonium acid fluoride (0.5) | Nitric acid (20) | 5- Aminotetrazoles (0.1) |
[embodiment 2]
The matrix being laminated on the glass substrate according to the order of titanium (30nm), copper (500nm) using eurymeric liquid resist
Upper 10 μm of line width of formation, the Resist patterns of 100 μm of opening portion, 10mm × 10mm is cut into by obtained substrate, as test film,
The test film is carried out by spray pattern under conditions of 35 DEG C, atomisation pressure 0.05MPa using product No.1~22 of the present invention
Pattern etches.For etch processes time, in each etchant, only implement the time for making wiring closet residue disappear, by the time
It is defined as " optimal etch time ".
[comparative example B]
The matrix being laminated on the glass substrate according to the order of titanium (30nm), copper (500nm) using eurymeric liquid resist
Upper 10 μm of line width of formation, the Resist patterns of 100 μm of opening portion, 10mm × 10mm is cut into by obtained substrate, as test film,
Figure is carried out to the test film by spray pattern using product No.1~6 are compared under conditions of 35 DEG C, atomisation pressure 0.05MPa
Case etches.Etch processes time is the optimal etch time.
[evaluation example 1]
For the test film obtained by embodiment 2 and comparative example B, by the top of light microscope validation test piece,
Thereby confirm that whether form fine rule.Here, the situation for forming fine rule is evaluated as into "○", the situation for not forming fine rule is evaluated as
“×”.In addition, using the section of scanning electron microscope viewing test piece, the width of the upper and lower part of fine rule is confirmed.Will
The situation that fine rule upper width is less than fine rule lower width is evaluated as " △ ", and it is wide that fine rule upper width is more than or equal into fine rule bottom
The situation of degree is evaluated as " △ ' ".It is explained, fine rule upper width is less than the situation (△) of fine rule lower width because fine rule is steady
It is fixed, therefore it is preferred that, fine rule upper width is more than or equal to the situation (△ ') of fine rule lower width because fine rule is easily damaged, therefore unexcellent
Choosing.As a result it is shown in table 3.
Table 3
| Composition | The observation result on fine rule top | The observation result of fine rule section | |
| Comparative example 1 | Compare product 1 | × | - |
| Comparative example 2 | Compare product 2 | × | - |
| Comparative example 3 | Compare product 3 | ○ | △ |
| Comparative example 4 | Compare product 4 | × | - |
| Comparative example 5 | Compare product 5 | ○ | △’ |
| Comparative example 6 | Compare product 6 | × | - |
| Evaluate example 1 | Product 1 of the present invention | ○ | △ |
| Evaluate example 2 | Product 2 of the present invention | ○ | △ |
| Evaluate example 3 | Product 3 of the present invention | ○ | △ |
| Evaluate example 4 | Product 4 of the present invention | ○ | △ |
| Evaluate example 5 | Product 5 of the present invention | ○ | △ |
| Evaluate example 6 | Product 6 of the present invention | ○ | △ |
| Evaluate example 7 | Product 7 of the present invention | ○ | △ |
| Evaluate example 8 | Product 8 of the present invention | ○ | △ |
| Evaluate example 9 | Product 9 of the present invention | ○ | △ |
| Evaluate example 10 | Product 10 of the present invention | ○ | △ |
| Evaluate example 11 | Product 11 of the present invention | ○ | △ |
| Evaluate example 12 | Product 12 of the present invention | ○ | △ |
| Evaluate example 13 | Product 13 of the present invention | ○ | △ |
| Evaluate example 14 | Product 14 of the present invention | ○ | △ |
| Evaluate example 15 | Product 15 of the present invention | ○ | △ |
| Evaluate example 16 | Product 16 of the present invention | ○ | △ |
| Evaluate example 17 | Product 17 of the present invention | ○ | △ |
| Evaluate example 18 | Product 18 of the present invention | ○ | △ |
| Evaluate example 19 | Product 19 of the present invention | ○ | △ |
| Evaluate example 20 | Product 20 of the present invention | ○ | △ |
| Evaluate example 21 | Product 21 of the present invention | ○ | △ |
| Evaluate example 22 | Product 22 of the present invention | ○ | △ |
As shown in Table 3, evaluation example 1~22 can form fine rule, and the width on fine rule top in whole samples
Less than the width of bottom.On the other hand, in comparative example 1~6, only comparative example 3 and 5 can form fine rule, can form fine rule top
The fine rule that width is less than lower width is only comparative example 3.
[embodiment 3]
The matrix being laminated on the glass substrate according to the order of titanium (30nm), copper (500nm) using eurymeric liquid resist
Upper 10 μm of line width of formation, the Resist patterns of 100 μm of opening portion, 10mm × 10mm is cut into by obtained substrate, as test film,
Using product No.2,4,5 and 16 of the present invention under conditions of 35 DEG C, atomisation pressure 0.05MPa by spray pattern to the test film
Carry out pattern etching.It is explained, etch processes time is implemented 30 seconds more than the optimal etch time.
[comparative example C]
The matrix being laminated on the glass substrate according to the order of titanium (30nm), copper (500nm) using eurymeric liquid resist
Upper 10 μm of line width of formation, the Resist patterns of 100 μm of opening portion, 10mm × 10mm is cut into by obtained substrate, as test film,
Using compare product No.3 under conditions of 35 DEG C, atomisation pressure 0.05MPa by spray pattern to the test film carry out pattern erosion
Carve.It is explained, etch processes time is implemented 30 seconds more than the optimal etch time.
[evaluation example 2]
For the test film obtained by embodiment 3 and comparative example C, by the top of light microscope validation test piece,
Thereby confirm that whether form fine rule.Here, the situation for forming fine rule is evaluated as into "○", the situation for not forming fine rule is evaluated as
“×”.In addition, using the section of scanning electron microscope viewing test piece, the width of the upper and lower part of fine rule is confirmed.Will
The situation that fine rule upper width is less than fine rule lower width is evaluated as " △ ", and it is wide that fine rule upper width is more than or equal into fine rule bottom
The situation of degree is evaluated as " △ ' ".It is explained, fine rule upper width is less than the situation (△) of fine rule lower width because fine rule is steady
It is fixed, therefore it is preferred that, fine rule upper width is more than or equal to the situation (△ ') of fine rule lower width because fine rule is easily damaged, therefore unexcellent
Choosing.As a result it is shown in table 4.
Table 4
| Composition | The observation result on fine rule top | The observation result of fine rule section | |
| Comparative example 8 | Compare product 3 | ×※1 | - |
| Evaluate example 23 | Product 2 of the present invention | ○ | △ |
| Evaluate example 24 | Product 4 of the present invention | ○ | △ |
| Evaluate example 25 | Product 5 of the present invention | ○ | △ |
| Evaluate example 26 | Product 16 of the present invention | ○ | △ |
※1：Represent that layers of copper is completely dissolved, disappeared.
As shown in Table 4, the layers of copper of comparative example 8 is completely dissolved.It will be appreciated that the process window for comparing product 3 is non-
It is often narrow.On the other hand, it is known that, evaluation example 23~25 can form fine rule in whole samples, and the width on fine rule top is less than
The width of bottom.
It will be appreciated that the situation that etchant of the invention more than the time is etched even in optimal etch
Under the quality of gained fine rule will not also be had an impact, therefore be the wide etchant of process window.
Claims (3)
1. etchant, it is used to together etch the stacked film comprising titanium mesentery and copper system film, it is characterised in that including
The aqueous solution, the aqueous solution contain：
(A) hydrogen peroxide：0.1~15 mass %；
(B) fluorine ion supply source：0.02~2 mass %；
(C) organic carboxyl acid：5~60 mass %；With
(D) there is the chemical combination of 6 circle heterocycles containing more than 1 nitrogen-atoms and containing 3 double bonds selected from azole compounds and in the structure
At least one kind of compound in thing：0.01~5 mass %,
Wherein, (D) is selected from azole compounds and has 6 circle heterocycles containing more than 1 nitrogen-atoms and containing 3 double bonds in the structure
At least one kind of compound in compound is at least one kind of in 5- amino -1H-TETRAZOLE and adenine.
2. the etchant described in claim 1, wherein, (C) organic carboxyl acid is citric acid.
3. engraving method, it is used to together etch the stacked film comprising titanium mesentery and copper system film, it is characterised in that as etching
Liquid composition, the etchant described in usage right requirement 1 or 2.
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| JP2013126506A JP6207248B2 (en) | 2013-06-17 | 2013-06-17 | Etching solution composition and etching method |
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| KR102080646B1 (en) * | 2013-04-12 | 2020-02-24 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Liquid composition used in etching copper- and titanium-containing multilayer film, etching method in which said composition is used, method for manufacturing multilayer-film wiring, and substrate |
| CN104532240A (en) * | 2014-12-31 | 2015-04-22 | 东莞市富默克化工有限公司 | Coarse micro-etching agent used in circuit board and preparation method of coarse micro-etching agent |
| TWI618817B (en) * | 2015-12-29 | 2018-03-21 | Daxin Materials Corporation | Etchant composition and etching method using thereof |
| CN105803459B (en) * | 2016-05-03 | 2019-01-15 | 苏州晶瑞化学股份有限公司 | A kind of microelectronics metal multilayer film etching solution and its application |
| KR102340997B1 (en) * | 2016-10-21 | 2021-12-21 | 가부시키가이샤 아데카 | Etching liquid composition and etching method |
| KR102570307B1 (en) * | 2016-10-31 | 2023-08-25 | 주식회사 이엔에프테크놀로지 | etching composition |
| CN108203829A (en) * | 2016-12-20 | 2018-06-26 | 群创光电股份有限公司 | The manufacturing method of etching solution and display |
| JP6746518B2 (en) * | 2017-03-10 | 2020-08-26 | 株式会社Adeka | Etching solution composition and etching method |
| CN107217263A (en) * | 2017-06-19 | 2017-09-29 | 江阴润玛电子材料股份有限公司 | A kind of semicon industry lug manufacturing process copper titanium corrosive liquid |
| CN111094627B (en) * | 2017-09-29 | 2022-04-05 | 松下知识产权经营株式会社 | Etching solution and etching concentrated solution for multilayer film and etching method |
| JP7105084B2 (en) * | 2018-03-30 | 2022-07-22 | ナガセケムテックス株式会社 | Etchant composition |
| JP7230908B2 (en) * | 2018-04-24 | 2023-03-01 | 三菱瓦斯化学株式会社 | Etching solution for copper foil and method for producing printed wiring board using the same, etching solution for electrolytic copper layer and method for producing copper pillar using the same |
| JP7377212B2 (en) * | 2018-10-17 | 2023-11-09 | 株式会社Adeka | Etching solution composition and etching method |
| CN111719157B (en) * | 2019-03-20 | 2024-06-07 | 易安爱富科技有限公司 | Etching composition and etching method using same |
| CN111334299B (en) * | 2020-03-26 | 2021-11-30 | 成都中电熊猫显示科技有限公司 | Etching liquid and preparation method thereof |
| CN114164003A (en) * | 2021-12-06 | 2022-03-11 | Tcl华星光电技术有限公司 | Etchant composition for display panel and etching method of display panel |
| CN114891509B (en) * | 2021-12-14 | 2023-05-05 | 湖北兴福电子材料股份有限公司 | High-selectivity buffer oxide etching solution |
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| KR100288575B1 (en) | 1997-04-02 | 2001-05-02 | 밍 루 | Device for changing vehicle system containing controller |
| KR100960687B1 (en) * | 2003-06-24 | 2010-06-01 | 엘지디스플레이 주식회사 | An etchant to etching a double layer with Cuor Cu-alloy |
| KR101495683B1 (en) * | 2008-09-26 | 2015-02-26 | 솔브레인 주식회사 | Cu or Cu/Mo or Cu/Mo alloy electrode etching liquid in Liquid Crystal Display system |
| KR101475954B1 (en) * | 2008-11-04 | 2014-12-24 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
| TWI480360B (en) * | 2009-04-03 | 2015-04-11 | Du Pont | Etchant composition and method |
| JP2011017052A (en) * | 2009-07-09 | 2011-01-27 | Adeka Corp | Wet etching system and patterning method for copper-containing material |
| JP5685204B2 (en) * | 2010-01-28 | 2015-03-18 | 三菱瓦斯化学株式会社 | Etching solution for copper / titanium multilayer thin film |
| KR101825493B1 (en) * | 2010-04-20 | 2018-02-06 | 삼성디스플레이 주식회사 | Etchant for electrode and method of fabricating thin film transistor array panel using the same |
| KR101270560B1 (en) * | 2010-11-12 | 2013-06-03 | 오씨아이 주식회사 | Composition for etching metal layer |
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