CN105765107B - Multilayer film etching solution and etching concentrate and engraving method - Google Patents
Multilayer film etching solution and etching concentrate and engraving method Download PDFInfo
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- CN105765107B CN105765107B CN201380081154.1A CN201380081154A CN105765107B CN 105765107 B CN105765107 B CN 105765107B CN 201380081154 A CN201380081154 A CN 201380081154A CN 105765107 B CN105765107 B CN 105765107B
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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
- C23F1/18—Acidic compositions for etching copper or alloys thereof
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Abstract
For by with a kind of liquid when the etching solution that the multilayer film of layers of copper and molybdenum layer is etched is used for volume production for it is important that：Vpg connection requires that the cross sectional shape at the edge after etching is positive cone rather than groove, and precipitate is not produced in etching solution.Because the multilayer film comprising layers of copper and molybdenum layer containing hydrogen peroxide, inorganic acid, acid organic acid, neutral organic acid, amines and hydrogen peroxide decomposing inhibitor does not contain azole compounds with etching solution, therefore the not reaction of formation thing between hydrogen peroxide, does not produce precipitate in etching solution.Moreover, preferable positive cone shape can be made in the cross sectional shape at the edge after etching.And then due to also not containing phosphorus compound, fluorine compounds, therefore environmental pressure is also light when discarded.
Description
Technical field
The present invention relates to the layers of copper used in the wiring purposes to liquid crystal, organic EL etc. flat-panel monitor and molybdenum layer
Used when multilayer film is etched, multilayer film etching solution and etching concentrate and engraving method.
Background technology
For liquid crystal, organic EL (electroluminescent, Electro-Luminescence) etc. flat-panel monitor (FPD)
TFT (thin film transistor (TFT), Thin film transistor), aluminium has been used as wiring material.In recent years, big picture and high-precision
The FPD popularizations of fineness, it is desirable to which used wiring material is the low material of resistance ratio aluminium.Therefore, in recent years, resistance ratio has been used
The low copper of aluminium is as wiring material.
When using copper as wiring material, the bonding force between substrate and the diffusion to semiconductor substrate this 2 can be produced
Problem.That is, in grid wiring in the case of use, even if using the larger sputtering method of the collision energy to base material, there is also
The insufficient situation of bonding force between the substrates such as glass.In addition, it can be produced in the case of use in source/drain wiring
The copper of attachment spreads to the silicon as substrate, can change the problem of electric design load of semiconductor.
In order to solve the problem, employ initially form molybdenum layer on substrate, semiconductor substrate in advance at present, then at it
The upper sandwich construction for forming layers of copper.
Being routed through for FPD is carried out wet etching to the multilayer film formed using sputtering method and formed.Because：Due to energy
Enough disposable large area are formed, therefore can shorten process.Herein, in the wet etching of wiring, it is important that following aspect.
(1) machining accuracy is highly consistent.
(2) the wiring section after processing is the positive cone of predetermined angular.
(3) due to containing copper ion in etching solution, therefore etching performance is not easily deteriorated (bath life length).
(4) generation of precipitate is lacked.
Machining accuracy as the 1st project is highly consistent to be, is not only carrying out wet etching but also is carrying out tiny area
The project necessarily required during processing.Wiring section as the 2nd project is shaped as, in the cloth for the FPD for forming large area in the lump
During line, in order to carry out the shape that certain wiring is formed and needed.Because the multilayer film of layers of copper and molybdenum layer is etched
When the part at edge can be formed from substrate with 30~60 degree of positive cone, even if occurring to etch the etch-rate of bad or copper and molybdenum
Balance it is different, can also ensure that the surplus that can ensure that product quality.
The problem of 3rd project is etching solution its shelf-life.In order to be etched the substrate of large area, it is necessary to largely lose
Carve liquid.These etching solutions can also recycle from the viewpoint of cost.During being able to maintain that its etching performance (life-span)
The cost of elder becomes cheap as far as possible.
In addition, the 4th project is not only to be used for the problem of maintaining Etaching device, also to be related to asking for the quality problems of product
Topic.When producing precipitate because of etching, it may occur that the hole with blockage or the spray nozzle for making sprinkling etching solution of Etaching device
Block.It is the reason for these phenomenons shut down as Etaching device, relevant with the rising of cost.In addition, precipitate is by etching
When liquid is attached on product, the reason for turning into short circuit, broken string, the problem of turning into the quality for being directly connected to product.
On layers of copper and the etching solution of the multilayer film of molybdenum layer, it was recently reported that contain at least 1 in neutral salt and organic acid
Etching solution (the patent document 1 of kind and hydrogen peroxide：Japanese Unexamined Patent Publication 2002-302780 publications (Japanese Patent 4282927)).
In addition, it was recently reported that the etching solution of following copper-molybdenum film：It is contained with ormal weight respectively：Hydrogen peroxide, organic acid, phosphorus
Hydrochlorate, the water-soluble cyclic amine compound as the 1st additive, as the 2nd additive containing a kind of in amino and carboxyl
Water soluble compound, fluorine compounds and deionized water (patent document 2：Japanese Unexamined Patent Publication 2004-193620 publication (Japanese Patents
No. 4448322)).
In addition, it was recently reported that molybdenum/copper containing hydrogen peroxide, organic acid, three azole compounds, fluorine compounds and ultra-pure water/
Etching solution (patent document 3 is used in the multiple film wiring of molybdenum nitride：Japanese Unexamined Patent Publication 2007-005790 publication (Japanese Patents 5111790
Number)).
In addition, also reported the following plural layers etching solution comprising layers of copper and molybdenum layer, it contains：(A) hydrogen peroxide；
(B) inorganic acid of fluorine atom is free of；(C) have selected from least one of butanedioic acid, glycolic, lactic acid, malonic acid and malic acid
Machine acid；(D) amines that carbon number 2~10 and amino and hydroxyl have in a manner of their total group numbers is more than two；
(E) 5- amino -1H-TETRAZOLE；And (F) stabilizer of hydrogen peroxide, pH are 2.5~5 (patent documents 4：Japanese Patent 5051323
Number).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2002-302780 publications (Japanese Patent 4282927)
Patent document 2：Japanese Unexamined Patent Publication 2004-193620 publications (Japanese Patent 4448322)
Patent document 3：Japanese Unexamined Patent Publication 2007-005790 publications (Japanese Patent 5111790)
Patent document 4：Japanese Patent 5051323
The content of the invention
Problems to be solved by the invention
Patent document 1 is only disclosed in the case of the mixed liquor of hydrogen peroxide and organic acid, if regulation hydrogen peroxide
Ratio, the then content that simultaneously can be etched copper and molybdenum, does not disclose the composition on specific etching solution completely.
Patent document 2,3 uses fluorine compounds in the composition.Therefore, only glass substrate, silicon substrate can be etched yet
The problem of, also produce etching solution it is discarded when environmental pressure become it is big the problem of.
Patent document 4 have studied the etching of the multilayer film of layers of copper and molybdenum layer in detail.But the etching solution of patent document 4
Composition produce in etching solution largely produce precipitate the problem of.
In addition, during using phosphorus compound, fluorine compounds as the composition of etching solution, the property as etching solution is readily available
Can, but it is big to the burden of environment when discarding.
The solution used to solve the problem
The present invention in view of above-mentioned problem and expect, its provide meet in [background technology] wiring of narration it is wet
The etchant for multilayer film point, comprising layers of copper and molybdenum layer that etched heavy is wanted.Specifically provide and do not produced in etching solution
Raw precipitate, and also little etching solution and its concentrate and engraving method are born to environment when discarding.
More specifically, multilayer film etching solution of the invention, the multilayer film include layers of copper and molybdenum layer, and its feature exists
In,
It contains hydrogen peroxide, inorganic acid, acid organic acid, neutral organic acid, amines and hydrogen peroxide and decomposes suppression
Preparation.
In addition, the present invention etching solution can when stored or conveying when volume do not increase ground, with the state structure of concentrate
Into.More specifically, multilayer film of the invention etching concentrate, the multilayer film include layers of copper and molybdenum layer, it is characterised in that
It contains inorganic acid, acid organic acid, neutral organic acid, amines, hydrogen peroxide decomposing inhibitor and water.
In addition, the multilayer film engraving method of the present invention, the multilayer film include layers of copper and molybdenum layer, it is characterised in that its
Including following process：
To containing inorganic acid, acid organic acid, neutral organic acid, amines, hydrogen peroxide decomposing inhibitor and water
Etching concentrate is concocted with water and hydrogen peroxide and concocts multilayer film etching solution；And
Aforenoted multi-layer film is set to be contacted with etching solution with processed substrate.
The effect of invention
For the etching solution of the present invention, the cross sectional shape of the wiring after etching is positive cone, in addition, even if carrying out overetch,
Its shape is also maintained.In addition, when hydrogen peroxide is used together, due to not contain the structure of the azole compounds of generation precipitate
Into, therefore precipitate is not produced in etching solution, this unfavorable condition of hole plug with blockage, spray nozzle is not produced.Cause
This, it is not necessary to stop the operating of Etaching device with being produced as reason of precipitate, the production that can be stablized.
In addition, the present invention etching concentrate compared to above-mentioned etching solution, due to not containing hydrogen peroxide and ormal weight
Water, therefore can volume do not increase and do not preserved or conveyed while rheological parameters' change with time does not also occur substantially.Further, since will etching
Concentrate and hydrogen peroxide are separately handled, thus can be easily adjusted because of use and the etching solution of composition change in concentration it is dense
Degree.
In addition, for the engraving method of the present invention, adjusted due to being concocted to above-mentioned etching concentrate and hydrogen peroxide
Etching solution is closed, it is contacted with processed substrate, therefore the etching solution of stable composition can be prepared at any time, the wiring of formation
Section has positive cone, even if carrying out overetch, can also carry out the etching that cone angle maintains the scope of appropriate angle.
In addition, the etching solution of the present invention therefore has due to not containing the materials such as phosphorus compound, chlorine compound, fluorine compounds
The advantages of light to the burden of environment when discarded.
Brief description of the drawings
Fig. 1 is the schematic diagram for representing the section by etching the wiring formed.
Embodiment
The etching solution of the present invention is illustrated below.It should be noted that the following description shows the etching of the present invention
One embodiment of liquid, following embodiment and embodiment can be changed in the scope for the purport for not departing from the present invention.This hair
Bright etching solution is characterised by, does not produce precipitate this point in etching solution.As be described hereinafter shown in embodiment, strong enlightenment analysis
The reason for going out thing is azole compounds and the reactant of hydrogen peroxide.Therefore, etching solution of the invention does not contain azole compounds.
In addition, in order to mitigate environmental pressure, phosphorus compound, fluorine compounds, chlorine compound are not contained yet.But to erosion
Carve performance, product quality does not have influence or it is discarded when environmental pressure as defined in various countries below benchmark in the case of, can be with
Contain.In addition, when measuring for as, can be construed to not contain.
<Hydrogen peroxide>
Etching for copper, copper are oxidized, form cupric oxide (CuO), by inorganic acid solution.In addition, the etching for molybdenum,
It is oxidized and turns into molybdenum oxide (MoO3), be dissolved in water.Hydrogen peroxide uses as the oxidant for aoxidizing copper and molybdenum.Peroxide
Change the mass % of 3.50 mass %~5.80 that hydrogen is preferably etching solution total amount.It should be noted that hydrogen peroxide is also referred to as " mistake
Water ".
<Inorganic acid>
In order to by the copper dissolution after oxidation, use inorganic acid.In order to not influence the baseplate materials such as glass, silicon, in addition to
Etching solution it is discarded when mitigate environmental pressure, without using phosphorus compound and fluorine compounds.In addition, also without using hydrochloric acid.Can be with
Suitably with nitric acid, sulfuric acid.Inorganic acid using relative to etching solution total amount as 0.01 mass % to 0.50 mass %, be preferably
0.02 mass % contains to 0.20 mass % scope.
<Organic acid>
Determination of Organic Acids mainly serves as the effect being adjusted to the angle of taper in the section of the wiring after etching.Separately
Outside, it is believed that also there is the function of the decomposition of suppression hydrogen peroxide to a certain degree.Determination of Organic Acids is using acid organic acid with
The combination of property organic acid.Alternatively, it is also possible to combine both acid organic acid and neutral organic acid.
As the organic acid that can be used, except the aliphatic carboxylic acid of carbon number 1~18, carbon number 6~10 aromatic carboxylic acid with
Outside, amino acid of carbon number 1~10 etc. can preferably be included.
As the aliphatic carboxylic acid of carbon number 1~18, can preferably include：Formic acid, acetic acid, propionic acid, lactic acid, glycolic, two
Glycolic acid, pyruvic acid, malonic acid, butyric acid, hydroxybutyric acid, tartaric acid, butanedioic acid, malic acid, maleic acid, fumaric acid, valeric acid, penta
Diacid, itaconic acid, adipic acid, caproic acid, adipic acid, citric acid, tricarballylic acid, trans-aconitic acid, enanthic acid, octanoic acid, laurate,
Myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, leukotrienes etc..
As the aromatic carboxylic acid of carbon number 6~10, can preferably include：Benzoic acid, salicylic acid, mandelic acid, O-phthalic
Acid, M-phthalic acid, terephthalic acid (TPA) etc..
In addition, the amino acid as carbon number 1~10, can preferably include carbamic acid, alanine, glycine, asparagus fern acyl
Amine, aspartic acid, methyl amimoacetic acid, serine, glutamine, glutamic acid, 4-Aminobutanoicacid, imino-diacetic butyric acid, arginine, bright ammonia
Acid, isoleucine, nitrilotriacetic acid etc..
, can be suitably with glycolic, aspartic acid, glutamic acid, lemon as acid organic acid among above-mentioned organic acid
Lemon acid.Especially by simultaneously be applied in combination glycolic, aspartic acid, glutamic acid these three, appropriate characteristic can be obtained.Need
It is noted that acid organic acid contains 1 mass % to 7 mass % preferably with respect to etching solution total amount.
In addition, in the case of using glycolic, aspartic acid, glutamic acid at the same time, relative to etching solution total amount, Ke Yihan
There is preferably 1 mass % to 5 mass %, more preferably 1.50 mass % to 2.50 mass % glycolic.In addition, relative to etching solution
Total amount, preferably 0.10 mass % to 1.00 mass %, more preferably 0.20 mass % to 0.50 mass % asparagus fern ammonia can be contained
Acid.In addition, relative to etching solution total amount, preferably 0.1 mass % to 1.0 mass %, more preferably 0.60 mass % can be contained extremely
0.90 mass % glutamic acid.
In addition, as neutral organic acid, can be suitably with glycine, alanine or Beta-alanine.In addition, relative to
Etching solution total amount, 0.10 mass % is preferably comprised to 3.00 mass % neutral organic acid.
In addition, glycolic and other a kind of acid organic acid or a kind of neutral organic acid can be combined beyond above-mentioned.
In this case, relative to etching solution total amount, preferably 1 mass % to 5 mass %, more preferably 1.50 mass % can be contained extremely
2.30 mass % glycolic.On the other hand, relative to etching solution total amount, can contain 0.10 mass % to 1.00 mass %,
Acid organic acids or neutral organic acid of the more preferably 0.3 mass % to 0.7 mass %.
<Amines>
Amines mainly serves as the pH regulations of etching solution., can be suitably with carbon number 2~10 as amines
Material.More specifically, can preferably include：Ethylenediamine, trimethylene diamine, tetra-methylenedimine, 1,2- propane diamine, 1,3-
Propane diamine, N, N- dimethyl -1,3- propane diamine, N, N- diethyl -1,3- propane diamine, 1,3- diaminobutanes, 2,3- diaminourea
Butane, five methylene diamine, 2,4- 1,5-DAPs, hexamethylene diamine, heptamethylene diamines, eight methylene diamine diamines,
Nine methylene diamines, N- methyl ethylenediamines, N, N- dimethyl-ethylenediamines, trimethyl ethylenediamine, NEED, N, N- diethyls
Base ethylenediamine, triethylethylenediamine, 1,2,3- triaminopropanes, hydrazine, three (2- amino-ethyls) amine, four (amino methyl) methane,
Diethylenetriamines, trien, tetren, the amine of seven ethylidene eight, the amine of nine ethylidene ten, diazabicylo ten
The polyamines such as one carbene；Monoethanolamine, N- methylethanolamines, N methyldiethanol amine, N- ehtylethanolamines, N- amino-ethyl ethanol
Amine, N- propyl group monoethanolamine, N- butylethanolamines, diethanol amine, triethanolamine, 1- amino -2- propyl alcohol, N- methyl isopropyls hydramine,
N- ethylisopropanolamines, N- propyl group isopropanolamine, 2- aminopropane -1- alcohol, N- methyl-2-aminos-propane -1- alcohol, N- ethyls -
2- amino-propan -1- alcohol, 1- aminopropane -3- alcohol, N- methyl isophthalic acids-aminopropane -3- alcohol, N- ethyl -1- aminopropanes -3-
Alcohol, 1- butylamine -2- alcohol, N- methyl isophthalic acids-butylamine -2- alcohol, N- ethyl -1- butylamine -2- alcohol, 2- butylamines -
1- alcohol, N- methyl-2-amino butane -1- alcohol, N- ethyl -2- butylamine -1- alcohol, 3- butylamine -1- alcohol, N- methyl -3-
Butylamine -1- alcohol, N- ethyl -3- butylamine -1- alcohol, 1- butylamine -4- alcohol, N- methyl isophthalic acids-butylamine -4- alcohol,
N- ethyl -1- butylamine -4- alcohol, 1- amino-2-methyl propane -2- alcohol, 2- amino-2-methyl propane -1- alcohol, 1- amino penta
Alkane -4- alcohol, 2- amino -4- methylpentane -1- alcohol, 2- aminohexane -1- alcohol, 3- aminoheptane -4- alcohol, 1- amino-octanes -2-
Alcohol, 5- amino-octane -4- alcohol, 1- aminopropane -2,3- glycol, 2- aminopropane -1,3- glycol, three (methylol) amino first
Alkane, 1,2- diaminopropanes -3- alcohol, 1,3- diaminopropanes -2- alcohol, 2- (2- amino ethoxies) ethanol, 2- (2- amino-ethyls
Amino) alkanolamine such as ethanol, diglycolamine, these can be used alone or combine a variety of use.Among these, especially
It is preferred that 1- amino -2- propyl alcohol.In addition, relative to etching solution total amount, 0.50 mass % to 2.00 mass %, more can be preferably comprised
1.00 mass % are preferably comprised to 1.90 mass % amines.
<Hydrogen peroxide decomposing inhibitor>
In the etching solution of the present invention, as oxidant, hydrogen peroxide is utilized.Decomposed because hydrogen peroxide carries out itself,
Therefore addition suppresses the decomposing inhibitor that it is decomposed.This is to extend the life-span of etching solution.As main hydrogen peroxide point
Inhibitor is solved, outside the urea system such as phenylurea, allylurea, 1,3- dimethyl ureas, thiocarbamide stabilizer of hydrogen peroxide, can preferably be enumerated
Go out：Lower alcohols such as phenyl acetamide, styrene glycol, 1- propyl alcohol, 2- propyl alcohol etc..
Especially particularly preferred phenylurea, it is further preferred that preferred compositions use phenylurea and 1- propyl alcohol.Hydrogen peroxide decomposes
When inhibitor is phenylurea, relative to etching solution total amount, preferably 0.05 mass % to 0.20 mass %, more preferably can be contained
0.07 mass % to 0.12 mass %.In addition, when being lower alcohol, 0.10 mass % to 2.00 mass %, more can be preferably comprised
It is preferred that 0.80 mass % to 1.20 mass %.
Think that these materials act on hydrogen peroxide, suppress the generation of free radical, so as to suppress the decomposition of hydrogen peroxide.Need
It is noted that relative to etching solution total amount, during containing the phenylurea for having more than 0.20 mass %, phenyl and hydroperoxidation,
Produce the precipitate different from the reactant of azole compounds and hydrogen peroxide.
<Chelating agent>
Cu, Mo are etched and are dissolved in etching solution, so as to promote the decomposition of hydrogen peroxide.Think chelating agent and Cu, Mo
Such metallic ion coordination, prevents metal ion from being contacted with hydrogen peroxide, so as to suppress the decomposition of hydrogen peroxide.Therefore, exist
In this specification, it is believed that chelating agent is hydrogen peroxide decomposing inhibitor.
As chelating agent, ethylenediamine tetra-acetic acid (EDTA), hydroxyethyliminodiacetic acid can be suitably used
(HIDA), ethylenediamine-N, N ' this amino carboxylic acid system chelating agent of-disuccinic acid (EDDS)., can be with excellent relative to etching solution total amount
Choosing contains 0.50 mass % to 1.00 mass %, the chelating agent preferably containing 0.60 mass % to 0.90 mass %.
<Polyethers>
Polyethers can be as the inhibitor of Cu etch-rate.During using polyethers, etching section cone angle diminishes, therefore can be with
It is suitable for the adjustment of cone angle.When having sulfuric acid especially as inorganic acid, effect is big., can be suitably with poly- as polyethers
Ethylene glycol (PEG).Relative to etching solution total amount, 0.10 mass % to 0.50 mass %, further preferably can be preferably comprised
0.20 mass % to 0.40 mass % polyethylene glycol.
<Copper ion>
For the etching solution of the present invention, it is thus identified that：It is dense according to Cu ions when etching carries out and contains Cu ions, Mo ions
The increase of degree, etch-rate change.Operating for Etaching device, due to so that the change of etch-rate fall into it is certain
The mode of allowed band adds etching concentrate, hydrogen peroxide controls, therefore preferably also falls into the permission in the state of new liquid
Scope.Therefore, Cu ions that can be containing prescribed limit in etching solution.Specifically, relative to etching solution total amount, contain
When 500ppm to 7000mmp, preferably 2000ppm to 4000ppm Cu ions, the change of readily estimated etch-rate, therefore it is preferred that.
<It is other>
In the etching solution of the present invention, in addition to these compositions, water can be added and do not hindering the model of etching performance
Enclose interior usually used various additives.For water, due to for the purpose of Precision Machining, it is therefore desirable for being the thing in the absence of foreign matter
Matter.For pure water or ultra-pure water when it is preferred.
<PH, temperature>
Scope of the etching solution of the present invention preferably in pH2~5, more preferably in pH3~4.5 uses.The etching solution of the present invention
It can be used between 18 DEG C to 40 DEG C.18 DEG C to 35 DEG C can be more preferably, be most preferably 20 DEG C to 32 DEG C.
<Preserve>
Hydrogen peroxide can be used in the etching solution of the present invention.Hydrogen peroxide carries out itself and decomposed.Therefore in etching solution
In contain hydrogen peroxide decomposing inhibitor.But when stored, hydrogen peroxide and other liquid can be retained separately.In addition, can
So that the raw material in addition to hydrogen peroxide and copper ion (to be referred to as " etching solution raw material ".) mixed with water and concoct etching solution raw material
Solution.The solution can be the water of the few ratio of the ratio of the water of the etching solution than being shown in aftermentioned embodiment.
The solution of etching solution raw material obtained from being concocted to etching solution raw material and water is referred to as " etching concentrate ".Erosion
Concentrate is carved compared with etching solution, without hydrogen peroxide, correspondingly volume is few, therefore is facilitated when preserving, conveying.Separately
Volume when outside, in order to further reduce preservation, conveying, " the etching height for reducing the water of " etching concentrate " can be made
Concentrate ".It is the etching concentrate containing 20% to 70% water to etch highly enriched liquid.Etching concentrate contains more than 70%
Water.Therefore, etching concentrate and hydrogen peroxide can be combined completion by etching solution of the invention, will can also be etched highly enriched
Liquid is combined completion with water and hydrogen peroxide.
<Engraving method>
Object using the etching solution of the present invention is the multilayer film for layers of copper/molybdenum layer that molybdenum is lower floor, copper is upper strata.Lower floor
Molybdenum layer thickness ratio upper strata copper thickness of thin.When being set to t0 by the thickness of lower floor, the thickness on upper strata is set into t1, it is configured to
T0/t1 scope is 0.01 to 0.2 scope.T0/t1 scope depart from the scope, Mo layers it is blocked up when, easily produce Mo layers
Residue, on the contrary when excessively thin, do not play the effect of the basalis as Cu layers.
In addition, the substrate and basalis for forming molybdenum layer and layers of copper are not particularly limited, using glass, silicon, non-crystalline silicon as generation
Table, or IGZO (amorphous semiconductor being made up of indium (Indium), gallium (Gallium), zinc (Zinc), oxygen (Oxide))
Deng metal oxide.
The etching solution of the present invention when stored (for hydrogen peroxide and can etch hydrogen peroxide and the highly enriched liquid of etching and water dense
Contracting liquid.) be retained separately, it is possibly realized so as to preserve.Therefore, during actual use, they are concocted to complete etching solution.It is right
In the method for blending, just do not limited as long as the concentration of final hydrogen peroxide is defined concentration.
One example is shown, blending in advance etches concentrate obtained from etching solution raw material is mixed in a certain amount of water.
Hydrogen peroxide is usually made the hydrogen peroxide of the high concentration of concentration of hydrogen peroxide than the etching solution of the present invention to supply.Therefore, with
Respective ormal weight is concocted to hydrogen peroxide and etching concentrate.The process is referred to as concocting the work of multilayer film etching solution
Sequence.Concocted alternatively, it is also possible to contrast the high highly enriched liquid of etching of etching concentrate concentration with water and hydrogen peroxide to prepare erosion
Carve liquid.
Copper ion can be when etching concentrate (or the highly enriched liquid of etching) or use with etching solution raw material and water concocting
Any stage when etching concentrate and dioxygen water concocting etching solution is mixed into.Of course, it is possible to it is added after etching solution is concocted.
It should be noted that when etching concentrate and hydrogen peroxide by additional filling in used etching solution, copper can be added without
Ion.Because copper ion in etching solution be present.
When being etched, as described above, in pH2~5, using etching solution under conditions of 18 DEG C to 40 DEG C.Therefore, it is preferable
Be etching object be also preheated to the temperature.The method for making processed substrate be contacted with etching solution is not limited especially
It is fixed.Etching solution can be sprayed to processed substrate from top as fountain, or processed substrate is immersed in etching
Method in the pond of liquid.The process is properly termed as the process for making multilayer film etching solution be contacted with processed substrate.
It should be noted that processed substrate is the following substrate of state, molybdenum layer (Mo layers) is laminated on the base materials such as glass
With layers of copper (Cu layers), pattern of the stacked film formed with the resist layer formed for pattern.
Embodiment
<The explanation of various evaluation methods>
For the etching solution of the present invention, with the cone in the section of the wiring after the etch-rate of copper and molybdenum (nm/min), etching
Angle (°), molybdenum layer groove, remain on substrate molybdenum layer (be referred to as " Mo residues ".), overetch patience, the presence or absence of precipitate, mistake
The project of hydrogen oxide decomposition rate (quality %/day) is evaluated.
Etch-rate determines as follows.First, sputtering is passed through on the Silicon Wafer formed with heat oxide film 100nm
Method, copper form monofilm respectively with 300nm, molybdenum with 150nm thickness.Make the copper film and molybdenum film and 30 DEG C of (also with good grounds comparisons
Example is 35 DEG C of situation.) etching solution contact 20 to 60 seconds.
Use sonde method resistrivity meter (the Mitsubishi Chemical of 4 terminal 4 for applying constant current mode
Analytech Co., Ltd. manufactures：MCP-T610 types) determine the resistance value for etching front and rear film.According to the change of the resistance value
Thickness Variation is calculated, calculates etch-rate.
Cone angle determines as follows.First, on the glass substrate by sputtering method with 20nm thickness by molybdenum layer film forming,
Continue layers of copper film forming to be made with 300nm thickness Cu/Mo multilayer membrane sample thereon.Patterning is formed in the layers of copper
For the resist of wiring shape, the base material as cone angle evaluation.That is, cone angle evaluation base material is by substrate, molybdenum layer and thereon
The resist layer of patterning in layers of copper and layers of copper is formed.Make the cone angle evaluation with base material in phase time appropriately etched
Between be immersed in etching solution to be etched.Sample after etching is cleaned, make its dry after, cut off wiring portion, see
Examine section.
The observation of section uses SEM (SEM, Scanning Electron Microscope) (Hitachi
Manufacture：SU8020 types), carried out under conditions of accelerating potential 1kV, 30000~50000 times.It should be noted that appropriate etching
For the time since etching untill film printing opacity.Visually to confirm at the time of film printing opacity.
Section shape is shown in Fig. 1.As shown in Fig. 1 (a), substrate 1 is with the angulation 5 of inclined plane 6 after etching
Cone angle (°).When cone angle is 30~60 °, it is judged as circle (zero).When outside for the angular range, it is judged as pitching (×).Need to illustrate
, it is successfully or qualified that " circle " refers to, " fork " refers to failure or unqualified.It is also identical in following evaluation.Need
It is noted that in Fig. 1 (a), Mo layers are represented with reference 3, Cu layers are represented with reference 2, resist layer is with accompanying drawing
Mark 4 represents.
The groove of molybdenum layer refers to first be etched than layers of copper between molybdenum layer 3 and substrate 1 as shown in Fig. 1 (b) reference 10
State (back taper).Evaluation can be carried out simultaneously in the evaluation of cone angle.For the groove of molybdenum layer, if 30000 times of SEM are arrived
It is not observed in 50000 times of observation, is judged as circle (zero), it was observed that is then judged as pitching (×).
For Mo residues, in the observation using light microscope and SEM, it is judged to pitching (×) if confirming to have residue,
Confirmation is not determined as circle (zero) then.It should be noted that light microscope is seen with 100 times or so of multiplying power using bright field
Examine and observed with dark field.In addition, SEM is observed with 30,000 times to 50,000 times.
For overetch patience (also referred to as " O.E. patience ".), to 2 times of times the time required to having carried out appropriate etching
Groove, the Mo residues of cone angle, molybdenum layer during etching are observed, and all " circle " evaluation is then judged as circle (zero).It is any
One is that " fork " judges then to be judged as " fork (×) ".
For the presence or absence of precipitate, after concocting etching solution, the stipulated time (several days) is placed in bottle at room temperature, visually to sentence
Whether precipitate is produced in disconnected bottle.When producing precipitate, with filter paper filtered etch liquid, remained in pure water cleaning different on filter paper
Thing, make its drying at room temperature, to resulting crystal, powder with FT-IR (Shimadzu Seisakusho Ltd. manufactures IR affinity), SEM-
EDX is analyzed (manufactured by the making of hole field).Sentence when being judged as circle (zero) when visual observation is less than precipitate, visually confirming
Break to pitch (×).
For etching solution, it is important that the cross sectional shape for not producing this point of precipitate and connecting up is appropriate, in order to extend tank liquor
Life-span, the decomposition rate of hydrogen peroxide also turn into important project.It is herein incorporated by reference, hydrogen peroxide decomposition rate also serves as commenting
Valency project is studied.
For hydrogen peroxide decomposition rate, titer reagent is set to potassium permanganate, uses automatic titration device
The GP-200 of manufacture (Mitsubishi Chemical Analytech Co., Ltd.s), to just concocting after etching solution and passing through
The concentration of hydrogen peroxide of (about 24h) is measured after stipulated time.Then, decomposition is calculated according to the variable quantity of concentration of hydrogen peroxide
Speed.
When the decrement of concentration of hydrogen peroxide after 24 hours (one day) is less than 1.0 mass %, circle (zero) is evaluated as, is
It is evaluated as pitching (×) during more than 1.0 mass %.It should be noted that even if hydrogen peroxide decomposition rate is fork, as long as other items
Mesh is circle, is referred to as the etching solution of the present invention.It should be noted that the evaluation on whole, although being unsatisfactory for circle
The condition of evaluation, but for extremely close to the value of boundary value when, be evaluated as triangle (△).
(embodiment 1)
To by the mass % of sulfuric acid 0.06, the mass % of glycolic 2.50, the mass % of aspartic acid 0.44, the matter of glutamic acid 0.87
Measure %, the mass % of 0.66 mass %, 1- amino -2- propyl alcohol of Beta-alanine 1.61, the mass % of phenylurea 0.11, ethylenediamine tetra-acetic acid
(also referred to as " EDTA " later.) 0.88 mass % formed etching solution raw material and the mass % of water 92.87 concocted, prepare etching
Concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 30 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 1 in etching solution entirety.
(embodiment 2)
To by the mass % of sulfuric acid 0.07, the mass % of glycolic 2.50, the mass % of aspartic acid 0.45, the matter of glutamic acid 0.88
Measure %, the mass % of 0.66 mass %, 1- amino -2- propyl alcohol of Beta-alanine 1.61, the mass % of phenylurea 0.11, ethylenediamine tetra-acetic acid
0.88 mass %, polyethylene glycol (also referred to as " PEG " later.) 0.33 mass % formed etching solution raw material and the matter of water 92.51
Amount % is concocted, and prepares etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 30 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 1 in etching solution entirety.
(embodiment 3)
To by the mass % of nitric acid 0.19, the mass % of glycolic 2.05, the mass % of aspartic acid 0.44, the matter of glutamic acid 0.90
Measure %, the mass % of 0.66 mass %, 1- amino -2- propyl alcohol of Beta-alanine 1.94, the mass % of phenylurea 0.11, ethylenediamine tetra-acetic acid
The etching solution raw material and the mass % of water 92.84 that 0.87 mass % is formed are concocted, and prepare etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 30 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 1 in etching solution entirety.
(embodiment 4)
To by the mass % of nitric acid 0.18, the mass % of glycolic 2.55, the mass % of aspartic acid 0.45, the matter of glutamic acid 0.91
Measure %, the mass % of 0.69 mass %, 1- amino -2- propyl alcohol of Beta-alanine 1.66, the matter of 0.11 mass %, 1- propyl alcohol of phenylurea 1.20
The etching solution raw material and the mass % of water 92.25 that amount % is formed are concocted, and prepare etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 30 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 1 in etching solution entirety.
(embodiment 5)
To by the mass % of sulfuric acid 0.05, the mass % of glycolic 2.47, the mass % of aspartic acid 0.44, the matter of glutamic acid 0.87
Measure %, the mass % of 1.17 mass %, 1- amino -2- propyl alcohol of glycine 1.61, the mass % of phenylurea 0.11, ethylenediamine tetra-acetic acid
The etching solution raw material and the mass % of water 92.41 that 0.87 mass % is formed are concocted, and prepare etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 30 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 1 in etching solution entirety.
(embodiment 6)
To by the mass % of sulfuric acid 0.07, the mass % of glycolic 2.46, the mass % of aspartic acid 0.44, the matter of glutamic acid 0.87
Measure the etching solution that %, the mass % of 1.74 mass %, 1- amino -2- propyl alcohol of Beta-alanine 1.58, the mass % of phenylurea 0.11 are formed
Raw material and the mass % of water 92.73 are concocted, and prepare etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 30 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 1 in etching solution entirety.
(embodiment 7)
To by the mass % of sulfuric acid 0.07, the mass % of glycolic 2.50, the mass %, 1- amino -2- propyl alcohol of citric acid 0.61
The etching solution raw material and the mass % of water 95.13 that 1.58 mass %, the mass % of phenylurea 0.11 are formed are concocted, and it is dense to prepare etching
Contracting liquid.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 30 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 1 in etching solution entirety.
(embodiment 8)
To by the mass % of sulfuric acid 0.07, the mass % of glycolic 2.27, the mass %, 1- amino -2- propyl alcohol of Beta-alanine 0.66
The etching solution that 1.94 mass %, the mass % of phenylurea 0.11, the mass % of ethylenediamine tetra-acetic acid 0.87, the mass % of polyethers 0.34 are formed
Raw material and the mass % of water 93.74 are concocted, and prepare etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 30 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 1 in etching solution entirety.
<Use the comparative example of azole compounds>
(comparative example 1)
To by the mass % of glycolic 5.62, the mass % of 5.20 mass %, 1- amino -2- propyl alcohol of glycine 1.31, phenylurea
The etching solution raw material and the mass % of water 87.63 that 0.11 mass %, 5- amino-mass % of 1H-TETRAZOLE 0.13 is formed are concocted, and are made
Standby etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 35 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 2 in etching solution entirety.
(comparative example 2)
To by the mass % of nitric acid 3.91, the mass % of 4.33 mass %, 1- amino -2- propyl alcohol of glycine 3.86, phenylurea
The etching solution raw material and the mass % of water 87.68 that 0.11 mass %, 5- amino-mass % of 1H-TETRAZOLE 0.11 is formed are concocted, and are made
Standby etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 35 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 2 in etching solution entirety.
(comparative example 3)
To by the mass % of glycolic 2.42, the mass % of 1.25 mass %, 1- amino -2- propyl alcohol of glycine 0.67, phenylurea
The etching solution raw material and the mass % of water 95.45 that 0.12 mass %, 5- amino-mass % of 1H-TETRAZOLE 0.09 is formed are concocted, and are made
Standby etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 35 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 2 in etching solution entirety.
(comparative example 4)
To by the mass % of glycolic 2.65, the mass % of glycine 1.00, the mass %, 1- amino -2- third of Beta-alanine 0.82
The etching solution raw material and water that the mass % of alcohol 0.39, mass %, the 5- amino of phenylurea 0.12-mass % of 1H-TETRAZOLE 0.12 are formed
94.90 mass % are concocted, and prepare etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 35 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 2 in etching solution entirety.
(comparative example 5)
To by the mass % of nitric acid 0.12, the mass % of 2.45 mass %, 1- amino -2- propyl alcohol of citric acid 2.62, phenylurea
The etching solution raw material and the mass % of water 94.44 that 0.08 mass %, 5- amino-mass % of 1H-TETRAZOLE 0.29 is formed are concocted, and are made
Standby etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 35 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 2 in etching solution entirety.
(comparative example 6)
To by the mass % of nitric acid 0.08, the mass % of glycolic 2.20, the mass % of malonic acid 3.98, the mass % of lactic acid 1.01,
The etching solution that the mass % of 1- amino-2- propyl alcohol 2.64, mass %, the 5- amino of phenylurea 0.12-mass % of 1H-TETRAZOLE 0.14 are formed
Raw material and the mass % of water 89.83 are concocted, and prepare etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 35 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 2 in etching solution entirety.
<Without using the comparative example of azole compounds>
(comparative example 7)
To by the mass % of glycolic 2.65, the mass % of 1.00 mass %, 1- amino -2- propyl alcohol of lactic acid 2.52, phenylurea
The etching solution raw material and the mass % of water 93.72 that 0.11 mass % is formed are concocted, and prepare etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 35 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 3 in etching solution entirety.
(comparative example 8)
To by the mass % of malonic acid 3.54, the mass % of 1.40 mass %, 1- amino -2- propyl alcohol of glycine 1.64, phenylurea
The etching solution raw material and the mass % of water 93.31 that 0.11 mass % is formed are concocted, and prepare etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 35 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 3 in etching solution entirety.
(comparative example 9)
To by the mass % of citric acid 3.61, the mass % of 1.43 mass %, 1- amino -2- propyl alcohol of glycine 1.64, phenylurea
The etching solution raw material and the mass % of water 93.21 that 0.11 mass % is formed are concocted, and prepare etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 35 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 3 in etching solution entirety.
(comparative example 10)
To by the mass % of lactic acid 4.73, the mass % of 1.39 mass %, 1- amino -2- propyl alcohol of glycine 1.72, phenylurea
The etching solution raw material and the mass % of water 92.05 that 0.11 mass % is formed are concocted, and prepare etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, with 35 DEG C of uses of liquid temperature.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 3 in etching solution entirety.
(comparative example 11)
To by the mass % of glycolic 2.80, the mass % of 1.41 mass %, 1- amino -2- propyl alcohol of glycine 1.25, phenylurea
The etching solution raw material and the mass % of water 94.43 that 0.11 mass % is formed are concocted, and prepare etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.
And then copper sulphate is added, prepared in a manner of copper ion concentration is 2000ppm.In addition, liquid temperature is with 35 DEG C of uses.Will be
The result of shared each constituent concentration and each evaluation item is shown in table 3 in etching solution entirety.
[table 1]
Etching condition
| Project | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Cu concentration | ppm | 2000 | 2000 | 2000 | 2000 | 2000 | 2000 | 2000 | 2000 |
| Temperature | ℃ | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
Evaluation result
| Assessment item | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Cu E.R. | nm/min | 250 | 228 | 260 | 270 | 228 | 214 | 360 | 237 |
| Mo E.R. | nm/min | 32 | 34 | 32 | 43 | 27 | 52 | 75 | 47 |
| Cone angle | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Mo grooves | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Mo residues | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| O.E. patience | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Precipitate | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Cross water decomposition speed | Quality %/day (25 DEG C) | ○ | ○ | ○ | ○ | ○ | △ | △ | △ |
[table 2]
Etching condition
| Project | Unit | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Cu concentration | ppm | 2000 | 2000 | 2000 | 2000 | 2000 | 2000 |
| Temperature | ℃ | 35 | 35 | 35 | 35 | 35 | 35 |
Evaluation result
| Assessment item | Unit | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Cu E.R. | nm/min | 220 | 254 | 214 | 205 | 202 | 293 |
| Mo E.R. | nm/min | 60 | 113 | 127 | 104 | 129 | 114 |
| Cone angle | × (big) | × (big) | × (big) | × (big) | × (big) | ○ | |
| Mo grooves | × | × | × | × | × (big) | ○ | |
| Mo residues | ○ | ○ | ○ | ○ | ○ | ○ | |
| O.E. patience | × | × | × | × | × | △ | |
| Precipitate | × | × | × | × | × | × | |
| Cross water decomposition speed | Quality %/day (25 DEG C) | ○ | ○ | ○ | ○ | ○ | ○ |
[table 3]
Etching condition
| Project | Unit | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 | Comparative example 11 |
| Cu concentration | ppm | 2000 | 2000 | 2000 | 2000 | 2000 |
| Temperature | ℃ | 35 | 35 | 35 | 35 | 35 |
Evaluation result
| Assessment item | Unit | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 | Comparative example 11 |
| Cu E.R. | nm/min | 269 | 563 | 257 | 409 | 257 |
| Mo E.R. | nm/min | 94 | - | 55 | 63 | 66 |
| Cone angle | × (small) | - | × (small) | × (small) | × (small) | |
| Mo grooves | ○ | - | ○ | ○ | ○ | |
| Mo residues | × | - | × | × | × | |
| O.E. patience | × | - | × | × | × | |
| Precipitate | ○ | ○ | ○ | ○ | ○ | |
| Cross water decomposition speed | Quality %/day (25 DEG C) | × | ○ | × | × | × |
<As a result>
Etching solution of the embodiment 1 to embodiment 8 for the present invention.Due to not containing azole compounds, thus with hydrogen peroxide
Between do not produce reactant, without precipitation portion.Acid organic acid has used this 3 kinds of glycolic, aspartic acid, glutamic acid simultaneously.
Among these, so that used the etching solution of EDTA or 1 propyl alcohol (embodiment 1 to 5), not only without precipitate, and bore
Angle, Mo grooves, Mo residues, any project of O.E. patience are circle evaluation.And then hydrogen peroxide decomposition rate again smaller than
0.1 mass %/day, has obtained desired result.
Further, since overetch patience is good, therefore can be tieed up untill 2 times of time from the time that appropriate etching is spent
It is etched with holding good cone angle.In addition, for the etching solution of these embodiments, even if Mo and Cu Film Thickness Ratio (t0/t1)
Different from the situation (20/300) of embodiment, but as long as Film Thickness Ratio when between 0.01 to 0.2, can also realize 30 ° to 60 °
Angle of taper.
Embodiment 6 is replaced into Beta-alanine from glycine compared with Example 5, by neutral organic acid, and does not add EDTA.
When eliminating EDTA, the decomposition rate (quality %/day) of hydrogen peroxide has exceeded 1.0 mass %/day.But the cloth after etching
The cross sectional shape of line is good.
Embodiment 7 and 8 is that Cu and Mo etching speed is adjusted using glycolic and citric acid or glycolic and Beta-alanine
Rate, the example of cone angle can be formed with appropriate scope.But hydrogen peroxide decomposition rate be just over 1.0 mass %/
My god.Accordingly, for the etching solution of the present invention, it may be said that at least contain glycolic as organic acid, and with hydrogen peroxide, inorganic
Acid, amines and stabilizer of hydrogen peroxide.Furthermore it is possible to contain chelating agent.
Comparative example 1 to comparative example 6 is the example containing azole compounds.As azole compounds, 5- amino -1H- four has been used
Azoles.As the effect using azole compounds, Cu etch-rate can be suppressed, and improve Mo etch-rate.Therefore, by obtaining
The balance with inorganic acid is obtained, cone angle can be controlled.
For comparative example 1 to 5, Mo etch-rate becomes big, cone angle becomes big.Comparative example 6 in order to adjustment sufficiently form
The etch-rate of copper is only improved, has used the mixing of glycolic, malonic acid, lactic acid.In comparative example 6, cone angle has obtained suitably
Result.But Mo etch-rate or fast, when carrying out overetch, slightly produce the groove of Mo layers.
Although composition of the comparative example 1 to 6 for so adjustable cone angle, azole compounds and hydrogen peroxide reacted and
Produce precipitate.
Comparative example 7 to 11 is the example for not containing azole compounds.As shown in comparative example 1 to 6, with inorganic acid and azole compounds
Combination have adjusted Cu and Mo etch-rate.Comparative example 7 to 11 is the situation without using azole compounds, it is desirable to is had by adjustment
Machine acid adjusts Cu and Mo etch-rate with amine.Amine has used 1- amino -2- propyl alcohol.
In comparative example 7, glycolic and lactic acid are used as organic acid, but cone angle is small.In comparative example 8, use
Malonic acid and glycine, but Cu etch-rate is too high, does not leave film.Comparative example 9 to 11 also changes neutral organic acid and acid
Property organic acid species, but Cu etch-rate is high, cone angle can not obtain good shape.But due to not containing azoles chemical combination
Thing, therefore without generation precipitate.
For embodiment, as demonstrated in comparative example 7 to 11, due to without using azole compounds, therefore precipitation is not produced
Thing.In addition, compared with comparative example 7 to 11, by using glycolic, aspartic acid and glutamic acid simultaneously, and optionally employ
EDTA or lower alcohol 1- propyl alcohol adjust the ratio of Cu and Mo etch-rate, can realize etched part appropriate cross sectional shape and
There is no the etching solution that precipitate, bath life are also grown.
Industrial applicability
The etching solution of the present invention makes regardless of FPD this kind of product such as liquid crystal display, plasma scope, organic EL
With formed on the substrates such as glass substrate, silicon substrate, amorphous silicon substrate, metal oxide substrate or formed by these materials
In the situation connected up obtained from molybdenum layer and layers of copper stacking on the basalis of formation, can widely it utilize.
Description of reference numerals
1 substrate
2 layers of copper
3 molybdenum layers
4 resists (layer)
5 cone angles
6 inclined planes
10 groove parts
Claims (13)
1. a kind of multilayer film etching solution, the multilayer film includes layers of copper and molybdenum layer, it is characterised in that its contain hydrogen peroxide,
Inorganic acid, acid organic acid, neutral organic acid, amines and hydrogen peroxide decomposing inhibitor, do not contain azole compounds, phosphatization
Compound and fluorine compounds.
2. multilayer film etching solution according to claim 1, it is characterised in that it also contains amino carboxylic acid system chelating agent.
3. multilayer film etching solution according to claim 1 or 2, it is characterised in that the inorganic acid is sulfuric acid or nitric acid
In it is at least one kind of.
4. multilayer film etching solution according to claim 1 or 2, it is characterised in that the acid organic acid includes ethanol
This 3 kinds of acid, aspartic acid, glutamic acid.
5. multilayer film etching solution according to claim 1 or 2, it is characterised in that the neutral organic acid is glycine
Any one of with Beta-alanine.
6. multilayer film etching solution according to claim 1 or 2, it is characterised in that the amines is 1- amino -2-
Propyl alcohol.
7. multilayer film etching solution according to claim 1 or 2, it is characterised in that the hydrogen peroxide decomposing inhibitor
For phenylurea or lower alcohol.
8. multilayer film etching solution according to claim 2, it is characterised in that amino carboxylic acid system chelating agent is optionally
Ethylenediamine tetra-acetic acid, hydroxyethyliminodiacetic acid, ethylenediamine-N, N '-disuccinic acid.
9. multilayer film etching solution according to claim 1 or 2, it is characterised in that it also contains polyethylene glycol.
10. multilayer film etching solution according to claim 1 or 2, it is characterised in that it is also containing 500~7000ppm's
Copper ion.
11. a kind of multilayer film etching concentrate, the multilayer film include layers of copper and molybdenum layer, it is characterised in that it contains inorganic
Sour, acid organic acid, neutral organic acid, amines, hydrogen peroxide decomposing inhibitor and water, do not contain azole compounds, phosphatization
Compound and fluorine compounds.
12. a kind of engraving method of multilayer film, the multilayer film includes layers of copper and molybdenum layer, it is characterised in that it includes following work
Sequence：
Etching concentrate is concocted with water and hydrogen peroxide and concocts multilayer film etching solution, the etching concentrate contains
Inorganic acid, acid organic acid, neutral organic acid, amines, hydrogen peroxide decomposing inhibitor and water, do not contain azole compounds,
Phosphorus compound and fluorine compounds；And
The multilayer film is set to be contacted with etching solution with processed substrate.
13. the engraving method of multilayer film according to claim 12, it is characterised in that make the multilayer film etching solution with
Scope that the process of processed substrate contact is 2 to 5 with the pH of etching solution in the multilayer film, the bar that liquid temperature is 18 DEG C to 35 DEG C
Carried out under part.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2013/006915 WO2015075765A1 (en) | 2013-11-25 | 2013-11-25 | Multilayer-film etchant, concentrated etchant, and etching method |
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| Publication Number | Publication Date |
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| CN105765107A CN105765107A (en) | 2016-07-13 |
| CN105765107B true CN105765107B (en) | 2017-12-19 |
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| CN201380081154.1A Active CN105765107B (en) | 2013-11-25 | 2013-11-25 | Multilayer film etching solution and etching concentrate and engraving method |
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| JP (1) | JP6128404B2 (en) |
| CN (1) | CN105765107B (en) |
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| JP6516214B2 (en) * | 2015-03-20 | 2019-05-22 | パナソニックＩｐマネジメント株式会社 | Etching solution for multilayer film, etching solution and etching method |
| CN107690488B (en) * | 2016-09-09 | 2019-03-01 | 松下知识产权经营株式会社 | Multilayer film etching solution and etching concentrate and engraving method |
| KR102404226B1 (en) * | 2016-10-31 | 2022-06-02 | 주식회사 이엔에프테크놀로지 | ETCHANT composition |
| CN108018556A (en) * | 2016-10-31 | 2018-05-11 | 易案爱富科技有限公司 | Etch combination |
| CN108130535B (en) * | 2016-12-01 | 2020-04-14 | 添鸿科技股份有限公司 | Etching solution for titanium-tungsten alloy |
| CN107012465B (en) * | 2017-03-28 | 2019-09-03 | 江苏和达电子科技有限公司 | A kind of copper etchant solution and its application |
| CN109280919B (en) * | 2017-07-20 | 2020-11-24 | 添鸿科技股份有限公司 | Etchant composition for copper-containing metal |
| CN108570678B (en) * | 2018-04-13 | 2021-01-26 | 惠州达诚微电子材料有限公司 | Metal etching liquid applied to copper-molybdenum film layer |
| CN108505042A (en) * | 2018-05-23 | 2018-09-07 | 深圳市百诣良科技发展有限公司 | A kind of the PCB thinned copper liquid of high speed and preparation method |
| CN108893741A (en) * | 2018-06-12 | 2018-11-27 | 江苏理工学院 | A kind of floride-free copper-molybdenum etching solution applied to thin film transistor line |
| CN109082663A (en) * | 2018-07-19 | 2018-12-25 | 深圳市华星光电半导体显示技术有限公司 | A kind of copper/molybdenum etching liquid composition and its application |
| CN108950557A (en) * | 2018-07-19 | 2018-12-07 | 深圳市华星光电半导体显示技术有限公司 | A kind of copper/molybdenum etching liquid composition and its application |
| JP7367700B2 (en) * | 2018-11-20 | 2023-10-24 | 三菱瓦斯化学株式会社 | Etching solution for selectively etching copper and copper alloys and method for manufacturing semiconductor substrates using the same |
| CN111117626B (en) * | 2019-12-28 | 2021-06-22 | 苏州天承化工有限公司 | Flash etching liquid medicine and preparation method and application thereof |
| EP4136273A4 (en) * | 2020-04-14 | 2024-05-01 | Entegris, Inc. | Method and composition for etching molybdenum |
| US11756797B2 (en) * | 2020-04-15 | 2023-09-12 | Tcl China Star Optoelectronics Technology Co., Ltd. | Etching method of copper-molybdenum film and array substrate |
| CN111850561B (en) * | 2020-07-29 | 2022-07-15 | 珠海市板明科技有限公司 | Copper corrosion accelerator and etching liquid medicine of sulfuric acid and hydrogen peroxide system |
| CN112351593B (en) * | 2020-11-16 | 2022-07-12 | 珠海联鼎化工设备有限公司 | OSP microetching pretreatment liquid for printed circuit board and microetching method |
| CN113026018B (en) * | 2021-03-01 | 2022-11-22 | 四川江化微电子材料有限公司 | Etching solution composition of copper-molybdenum alloy and etching method |
| CN115948745A (en) * | 2022-12-28 | 2023-04-11 | 武汉迪赛环保新材料股份有限公司 | Etching solution for TFT-LCD panel and application thereof in etching multi-layer copper process panel containing alloy layer |
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| WO2015075765A1 (en) | 2015-05-28 |
| CN105765107A (en) | 2016-07-13 |
| JPWO2015075765A1 (en) | 2017-03-16 |
| JP6128404B2 (en) | 2017-05-17 |
| TW201533272A (en) | 2015-09-01 |
| TWI624565B (en) | 2018-05-21 |
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