CN106255777B - Multilayer film etching solution comprising molybdenum and copper, etching concentrate and engraving method - Google Patents
Multilayer film etching solution comprising molybdenum and copper, etching concentrate and engraving method Download PDFInfo
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- CN106255777B CN106255777B CN201580021009.3A CN201580021009A CN106255777B CN 106255777 B CN106255777 B CN 106255777B CN 201580021009 A CN201580021009 A CN 201580021009A CN 106255777 B CN106255777 B CN 106255777B
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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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- 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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Abstract
In the etching solution being etched using a kind of liquid to the multilayer film of molybdenum and copper, it is expected that mixed organic acid uses in water is crossed.Organic acid oxidation is decomposed and is generated oxalic acid however, crossing water, therefore the problem for the precipitate that a large amount of cupric oxalates are produced in etching solution be present.Multilayer film etching solution comprising molybdenum and copper is combined so as to suppress the generation of cupric oxalate by aluminium ion with oxalic acid, therefore, precipitate will not be produced in etching solution, the multilayer film etching solution comprising molybdenum and copper is characterised by, is contained：Hydrogen peroxide, acid organic acid, amines, hydrogen peroxide decomposing inhibitor, azole and the anti-precipitation agent comprising aluminium salt.Moreover, the cross sectional shape at the edge after etching can form preferable positive cone shape.
Description
Technical field
The present invention relates to the multilayer of the copper used in the wiring purposes to liquid crystal, organic EL etc. flat-panel monitor and molybdenum
Used when 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 film on a semiconductor substrate in advance at present, then in shape thereon
Into the sandwich construction of copper film.
Being routed through for FPD is carried out wet etching to the multilayer film formed using sputtering method and formed.Because：Due to
It large area can disposably be formed, therefore process can be shortened.Herein, in the wet etching of wiring, it is important that with lower section
Face.
(1) machining accuracy is highly consistent.
(2) the wiring section after processing is the positive cone of predetermined angular.
(3) due to comprising copper ion, therefore etch-rate will not change (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
Processing when the project that necessarily requires.Wiring section as the 2nd project is shaped as, and is forming the FPD's of large area in the lump
During wiring, in order to carry out the shape that certain wiring is formed and needed.Because the side being etched of the multilayer film of copper and molybdenum
When the part of 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 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 be only maintain Etaching device the problem of, also to be related to the quality problems of product the problem of.
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 is blocked up
Plug.These phenomenons turn into Etaching device stop the reason for, it is relevant with the rising of cost.In addition, precipitate adheres to by etching solution
When on product, turn into the reason for short-circuit, breaking, the problem of turning into the quality for being directly connected to product.
Etching solution on copper and the multilayer film of molybdenum, it was recently reported that containing at least one kind of in neutral salt and organic acid and
The etching solution (patent document 1) of hydrogen peroxide.
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).
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.
In addition, it is also reported that layers of copper and the plural layers etching solution of molybdenum layer are included as follows, 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).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2002-302780 publications (Japanese Patent No. 4282927)
Patent document 2：Japanese Unexamined Patent Publication 2004-193620 publications (Japanese Patent No. 4448322)
Patent document 3：Japanese Unexamined Patent Publication 2007-005790 publications (Japanese Patent No. 5111790)
Patent document 4：International publication number WO2011/099624 (Japanese Patent No. 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, then the content that the etch-rate of copper and molybdenum can be made to be etched in the same manner, do not disclose completely on specific etching
The composition of liquid.
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 copper and molybdenum in detail.But the composition of the etching solution of patent document 4 produces
The problem of precipitate is largely produced in etching solution.What particularly amount of precipitation was most is the precipitate for being light blue color.It utilizes XRD (X
X ray diffraction analysis x device), FTIR (FFIR device) confirm as cupric oxalate.
However, oxalic acid is not included in patent document 4.However but generation cupric oxalate is considered the reasons why following.
Know that the oxidizing force of hydrogen peroxide is strong.The organic acids such as malonic acid, glycolic are included in the etching solution of patent document 4.Hydrogen peroxide leads to
Cross and are carried out by oxidation Decomposition and generates oxalic acid for these organic acids.And think, the oxalic acid and the Cu in etching solution2+Ion forms network
Compound generates cupric oxalate.
Cupric oxalate lacks Cu because solubility is low, therefore by the oxidation Decomposition of organic acid and the amount generated2+Ion there is also
When, positively it is changed into precipitate.On the other hand, when containing organic acid in the etching solution comprising hydrogen peroxide, it is known to be suitable for
The effect for the cone angle that the boundary member adjusted in the copper film being etched is formed.Therefore, comprising hydrogen peroxide and having in etching solution
Expectation can also suppress the composition of the generation of cupric oxalate on the basis of machine acid.
The solution used to solve the problem
The present invention be in view of above-mentioned problem and expect, there is provided：Meet the wet method to the wiring described in [background technology]
The etchant of the copper for the aspect that etched heavy is wanted and 2 tunics of molybdenum.Especially it is to provide：Contain hydrogen peroxide in etching solution
With the etching solution that cupric oxalate (precipitate) will not be also produced on the basis of organic acid.
The etching solution of the present invention is based on following technical concept：Given birth to even if containing in etching solution by the oxidation Decomposition of organic acid
Complex compound and the high material of solubility are also easily formed with oxalic acid compared with copper into oxalic acid, so as to suppress as caused by cupric oxalate
The generation of precipitate.The present inventor tests by numerous studies, as a result finds：Oxalic acid aluminium easy network compared with cupric oxalate
Compound, and solubility is also high, so as to complete the present invention.
More specifically, the multilayer film etching solution comprising layers of copper and molybdenum layer of the invention is characterised by, is contained：
Hydrogen peroxide,
Acid organic acid,
Amines,
Hydrogen peroxide decomposing inhibitor,
Azole and
Anti- precipitation agent comprising aluminium salt.
In addition, the etching solution of the present invention can be in a manner of volume will not increase when to preserve or when conveying by the shape of concentrate
State is formed.More specifically, the etching concentrate of the multilayer film comprising layers of copper and molybdenum layer of the invention is characterised by, described more
Tunic includes molybdenum and copper,
The etching concentrate contains：
Acid organic acid,
Amines,
Hydrogen peroxide decomposing inhibitor,
Azole,
Anti- precipitation agent comprising aluminium salt and
Water.
In addition, the multilayer film engraving method comprising layers of copper and molybdenum layer of the present invention is characterised by, including following process：
Allotment etching concentrate, water and hydrogen peroxide, so as to allocate the process of multilayer film etching solution,
The etching concentrate contains：Acid organic acid,
Amines,
Hydrogen peroxide decomposing inhibitor,
Azole,
Anti- precipitation agent comprising aluminium salt and
Water；And
The process for making aforenoted multi-layer film etching solution be contacted with processed substrate.
The effect of invention
The multilayer film of the present invention is contained with etching solution：Hydrogen peroxide, acid organic acid, amines, hydrogen peroxide decompose
Inhibitor, azole and the anti-precipitation agent comprising aluminium salt, therefore, organic acid (acid organic acid), which is oxidized, to be decomposed, even if as a result raw
Also it is changed into oxalic acid aluminium into oxalic acid, exists with the state being dissolved in etching solution.That is, the precipitate of cupric oxalate will not be produced.
As a result, there is no the generation of precipitate in etching solution, will not produce with blockage, the hole plug sprayed etc no
Good situation.It is therefore not necessary to stop Etaching device as reason using such unfavorable condition, the production that can be stablized.
In addition, as acid organic acid, comprising at least one kind of in glycolic, malonic acid, lactic acid, therefore, the cloth being etched
The cross sectional shape of line is changed into positive cone, in addition, the shape is also maintained even if overetch.
In addition, the multilayer film of the present invention uses etching concentrate due to excluding hydrogen peroxide and ormal weight from above-mentioned etching solution
Water, therefore, volume will not increase, in addition, will not also cause rheological parameters' change with time substantially, can preserve or convey.
In addition, the multilayer film engraving method of the present invention allocates erosion due to allocating above-mentioned etching concentrate and hydrogen peroxide
Liquid is carved, it is contacted with processed substrate, therefore, can etch concentrate and hydrogen peroxide by rear addition makes to adjust basis
With and change etching solution composition, bath life can be extended.
Brief description of the drawings
Fig. 1 is the schematic diagram in the section of wiring for showing to be etched.
Embodiment
The multilayer film of the present invention is illustrated with etching solution below.It should be noted that the following description shows this hair
One embodiment of bright etching solution, following embodiment and implementation can be changed in the scope for the purport for not departing from the present invention
Example.The multilayer film etching solution of the present invention is characterised by, does not produce precipitate this point in etching solution.
For precipitate azury it is cupric oxalate the reason for precipitate as be described hereinafter shown in embodiment.For the present invention's
Multilayer film etching solution, even if organic acid, which is oxidized, decomposes generation oxalic acid, the high oxalic acid aluminium of solubility is also formed, thus, is suppressed
The generation of precipitate.
＜ hydrogen peroxide ＞
Etching for copper, copper is oxidized, forms cupric oxide (CuO), and is dissolved by sour (organic acid).In addition, for molybdenum
Etching, molybdenum be oxidized and turn into molybdenum oxide (MoO3), be dissolved in water.Hydrogen peroxide comes as by the oxidant of copper and molybdenum oxidation
Use.Hydrogen peroxide is preferably the mass % of 4.0 mass %~5.8 of etching solution total amount.It should be noted that hydrogen peroxide is for example
Water (hydrogen peroxide) of crossing as concentration 35% is supplied to.
＜ organic acids ＞
Organic acid has following effect：Copper film is etched, and adjusts the taper in the section for the wiring being etched.In addition
Think, the function of the decomposition also with a certain degree of suppression hydrogen peroxide.Organic acid uses acid organic acid.Need what is illustrated
It is that in multilayer film etching solution of the invention, as anti-precipitation agent described later, neutral organic acid can also be included.
As organic acid, aliphatic carboxylic acid except carbon number 1~18, in addition to the aromatic carboxylic acid of carbon number 6~10 can be with
It is preferred that enumerate：Amino acid of carbon number 1~10 etc..
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, caproic acid, adipic acid, citric acid, tricarballylic acid, trans-aconitic acid, enanthic acid, octanoic acid, laurate, nutmeg
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..
In above-mentioned organic acid, as acid organic acid, it can be adapted to utilize glycolic, malonic acid, lactic acid.Especially by
Simultaneously be applied in combination glycolic, malonic acid, lactic acid these three, suitable characteristic can be obtained.It is it should be noted that preferable
It is, comprising relative to the acid organic acid that etching solution total amount is 1 mass % to 7 mass %.
It should be noted that during using glycolic, malonic acid, lactic acid, glycolic and malonic acid are relative to etching solution total amount
Preferably 1 mass % to 5 mass %, lactic acid are preferably 0.1 mass % to 1.0 mass % relative to etching solution total amount.
＜ amines ＞
Amines undertakes the pH regulations of etching solution.As amines, the material using carbon number 2~10 can be adapted to.
More specifically, can preferably include：Ethylenediamine, trimethylene diamine, tetra-methylenedimine, 1,2- propane diamine, 1,3- the third two
Amine, N, N- dimethyl -1,3- propane diamine, N, N- diethyl -1,3- propane diamine, 1,3- diaminobutanes, 2,3- diaminobutanes,
Five methylene diamine, 2,4- 1,5-DAPs, hexamethylene diamine, heptamethylene diamines, eight methylene diamines, nine methylene two
Amine, N- methyl ethylenediamines, N, N- dimethyl-ethylenediamines, trimethyl ethylenediamine, NEED, N, N- diethyl ethylenediamines,
Triethylethylenediamine, 1,2,3- triaminopropanes, hydrazine, three (2- amino-ethyls) amine, four (amino methyl) methane, diethylidene three
Amine, trien, tetren, the amine of seven ethylidene eight, the amine of nine ethylidene ten, diazabicylo endecatylene etc. are more
Amine；Monoethanolamine, N- methylethanolamines, N methyldiethanol amine, N- ehtylethanolamines, N- amino ethyl ethanolamines, N- propyl group second
Hydramine, N- butylethanolamines, diethanol amine, triethanolamine, 1- amino -2- propyl alcohol, N- methyl isopropyls hydramine, N- ethylisopropyl alcohol
Amine, N- propyl group isopropanolamine, 2- aminopropane -1- alcohol, N- methyl-2-aminos-propane -1- alcohol, N- ethyl -2- amino-propans -
1- alcohol, 1- aminopropane -3- alcohol, N- methyl isophthalic acids-aminopropane -3- alcohol, N- ethyl -1- aminopropane -3- alcohol, 1- amino fourths
Alkane -2- alcohol, N- methyl isophthalic acids-butylamine -2- alcohol, N- ethyl -1- butylamine -2- alcohol, 2- butylamine -1- alcohol, N- methyl -
2- butylamine -1- alcohol, N- ethyl -2- butylamine -1- alcohol, 3- butylamine -1- alcohol, N- methyl -3- butylamines -1-
Alcohol, N- ethyl -3- butylamine -1- alcohol, 1- butylamine -4- alcohol, N- methyl isophthalic acids-butylamine -4- alcohol, N- ethyl -1- ammonia
Base butane -4- alcohol, 1- amino-2-methyl propane -2- alcohol, 2- amino-2-methyl propane -1- alcohol, 1- aminopentane -4- alcohol, 2-
Amino -4- methylpentane -1- alcohol, 2- aminohexane -1- alcohol, 3- aminoheptane -4- alcohol, 1- amino-octane -2- alcohol, 5- amino are pungent
Alkane -4- alcohol, 1- aminopropane -2,3- glycol, 2- aminopropane -1,3- glycol, three (methylol) aminomethanes, 1,2- diaminourea
Propane -3- alcohol, 1,3- diaminopropanes -2- alcohol, 2- (2- amino ethoxies) ethanol, 2- (2- aminoethylaminos) ethanol, two
The alkanolamines such as glycol amine, these can be used alone or combine a variety of use.Among these, particularly preferred 1- amino-
2- propyl alcohol.In addition, 0.5 mass % is preferably comprised to 2.0 mass % amines relative to etching solution total amount.
＜ hydrogen peroxide decomposing inhibitors ＞
In the multilayer film etching solution of the present invention, as oxidant, hydrogen peroxide is utilized.Because hydrogen peroxide is carried out certainly
Status solution, therefore add and suppress its decomposing inhibitor decomposed.Also referred to as cross water stabilizer.This is to extend etching solution
Life-span.As main hydrogen peroxide decomposing inhibitor, except the urea system such as phenylurea, allylurea, 1,3- dimethyl ureas, thiocarbamide mistake
Outside hydrogen oxide stabilizer, it can preferably include：Lower alcohols such as phenyl acetamide, styrene glycol, 1- propyl alcohol, 2- propyl alcohol etc..
Wherein particularly preferred phenylurea, it is further preferred that preferred compositions use phenylurea and 1- propyl alcohol.Preferably with respect to erosion
Carve liquid total amount and contain 0.5 mass % to 2.0 mass % hydrogen peroxide decomposing inhibitor.Think, these materials act on peroxide
Change hydrogen, suppress the generation of free radical so as to suppress the decomposition of hydrogen peroxide.It should be noted that contain relative to etching solution total amount
During phenylurea more than 0.2 mass %, phenyl reacts with hydrogen peroxide, generates the reaction product with azole and hydrogen peroxide
Different precipitates.
＜ azoles ＞
In the multilayer film etching solution of the present invention, in order to suppress Cu etch-rate, removing Mo residue and contain azole.
As azole, can be adapted to utilize triazole type, four azoles, imidazoles, thiazoles etc..More specifically, following thing can be enumerated
Matter.As triazole type, can be adapted to utilize 1H- BTAs, 5- methyl isophthalic acid H- BTAs, 3- amino -1H- triazoles etc..
As four azoles, can be adapted to using 1H-TETRAZOLE, 5- methyl isophthalic acid H- tetrazoliums, 5- phenyl -1H-TETRAZOLE, 5- amino -
1H-TETRAZOLE etc..In addition, as imidazoles, can be adapted to utilize 1H- imidazoles, 1H- benzimidazoles etc..In addition, as thiazoles,
It can be adapted to utilize 1,3- thiazoles, 4- methylthiazols etc..It should be noted that wherein, effect of four azoles to suppression etch-rate
Fruit is high, particularly preferred 5- amino -1H-TETRAZOLE.
The anti-precipitation agent ＞ of ＜
When containing organic acid in the etching solution based on hydrogen peroxide described above, the wiring being etched can be adjusted and cut
The taper in face.However, organic acid is oxidized decomposition because of hydrogen peroxide, oxalic acid is generated.By the oxalic acid and it is etched and is present in
Copper ion generation cupric oxalate in etching solution, is changed into precipitate.Aluminium ion easily forms complex compound compared with copper with oxalic acid, and
Solubility is higher than cupric oxalate.
Therefore, in etching solution of the invention, even if containing aluminium salt in advance, copper ion is produced by etching, will not be also changed into
Precipitate (cupric oxalate).As aluminium salt, can be adapted to utilize inorganic salts, aluctyl, the acetic acid such as aluminum sulfate, aluminum nitrate, aluminium chloride
Organic salts such as aluminium, aluminium carbonate etc..
＜ copper ions ＞
For the multilayer film etching solution of the present invention, it is thus identified that：When etching carries out and contains Cu ions, Mo ions, according to
The increase of Cu ion concentrations, etch-rate change.Operating for Etaching device, due to so that the change of etch-rate falls
The mode for entering certain allowed band adds etching concentrate, hydrogen peroxide is controlled, therefore preferably also fallen in the state of new liquid
Enter the allowed band.Therefore, Cu ions that can be containing prescribed limit in etching solution.Specifically, if 500ppm extremely
During 7000ppm, preferably 2000ppm to 4000ppm, the change of readily estimated etch-rate, therefore it is preferred that.
Other ＞ of ＜
In the multilayer film etching solution of the present invention, in addition to these compositions, water can be added and do not hindering to etch
Usually used various additives in the range of performance.For water, due to for the purpose of Precision Machining, it is therefore desirable for in the absence of
The material of foreign matter.For pure water or ultra-pure water when it is preferred.
＜ pH, temperature ＞
The multilayer film of the present invention is preferably used with etching solution in the range of pH2~6, more preferably pH3~4.5.In addition, erosion
Carving liquid can use between 20 DEG C to 40 DEG C.More preferably 25 DEG C to 35 DEG C, most preferably 30 DEG C to 35 DEG C.
＜ preserves ＞
The multilayer film of the present invention uses hydrogen peroxide with etching solution.Hydrogen peroxide carries out itself and decomposed.Therefore, in etching solution
Include hydrogen peroxide decomposing inhibitor.However, when preserving, hydrogen peroxide and other liquid can be retained separately.In addition, also may be used
Eliminate the raw material (be referred to as " etching solution raw material ") of water and copper ion only to retain and preserved.It should be noted that etching solution
There may be liquid charging stock and powder material in raw material.That is, multilayer film etching solution of the invention can merge etching solution raw material,
Water and hydrogen peroxide are completed.
Alternatively, it is also possible in advance mix etching solution raw material and water, the solution of etching solution raw material is made.The solution can contain
The water of the ratio fewer than the ratio of the water of the etching solution shown in embodiment described later.By by the etching of etching solution raw material and water making
The solution of liquid raw material is referred to as " etching concentrate ".Concentrate is etched compared with etching solution, the small volume without hydrogen peroxide, because
This, facilitates when preserving, conveying.Therefore, multilayer film etching solution of the invention can combine etching concentrate, water and hydrogen peroxide
And complete.
＜ engraving methods ＞
It is with the object of etching solution using multilayer film of the invention：Molybdenum is changed into lower floor, copper be changed into upper strata copper/molybdenum multilayer
Film.The thickness of thin of the copper on the thickness ratio upper strata of the molybdenum of lower floor.The thickness of lower floor is set to t0, when the thickness on upper strata is set to t1, t0/
T1 scope is the composition of 0.01 to 0.2 scope.T0/t1 scope exceedes the scope, when Mo layers are blocked up, easily produces Mo layers
Residue, on the contrary, when excessively thin, effect of the Cu layers as basalis can not be played.
For the multilayer film etching solution of the present invention, during preservation, by advance by hydrogen peroxide and etching solution raw material and
Water is retained separately, and is possibly realized so that preserving.Therefore, during actual use, they is allocated and completes etching solution.For allotment
Method, as long as the concentration of final hydrogen peroxide be changed into as defined in concentration just do not limit.
One is shown, the previously prepared etching concentrate that etching solution raw material is mixed with a certain amount of water.Hydrogen peroxide
Generally supplied with the high concentration of the concentration of hydrogen peroxide of the multilayer film etching solution than the present invention.Therefore, ormal weight is allocated respectively
Hydrogen peroxide and etching concentrate.The process can be referred to as to the process for allocating multilayer film etching solution.
Copper ion can be when with etching solution raw material and water allotment etching concentrate or with etching concentrate and hydrogen peroxide
It can be mixed into when allocating etching solution.It can certainly be added after etching solution is allocated.It should be noted that using
In etching solution when additional addition etching concentrate and hydrogen peroxide, copper ion can also be added without.This is because, copper ion is
It is present in etching solution.
When being etched, as described above, etching solution is used under conditions of pH2~6,20 DEG C to 40 DEG C.Therefore, it is desirable to
Etching is also heated at the temperature by object.The method for making processed substrate be contacted with etching solution is not particularly limited.Can be with
As fountain, etching solution is spread processed substrate from top, or can also be processed substrate is impregnated in erosion
The method for carving the pond of liquid.The process for making multilayer film etching solution be contacted with processed substrate can also be referred to as.
It should be noted that processed substrate refers to, molybdenum layer and layers of copper are laminated on the base materials such as glass and in the stacked film
On formed for pattern formed protective agent pattern state substrate.
Embodiment
The explanation ＞ of the various evaluation methods of ＜
For the multilayer film etching solution of the present invention, the etch-rate of copper and molybdenum (is also recited as " CuE.R. " respectively
" MoE.R. ") (nm/ minutes), the cone angle (°) in section for the wiring being etched, the undercutting of molybdenum layer, the molybdenum layer that remains on substrate (claim
For " Mo residues "), overetch patience, the presence or absence of precipitate, hydrogen peroxide decomposition rate (quality %/day) project in commented
Valency.
Etch-rate is measured as described below.First, by sputtering method, in the silicon formed with heat oxide film 100nm
Monofilm is formed respectively for 150nm thickness using copper as 300nm, molybdenum on wafer.Make the copper film and molybdenum film with 30 DEG C (compared with
Example also has 35 DEG C of situation) etching solution contact 20 to 60 seconds.
Use sonde method resistrivity meter (the Mitsubishi Chemical of 4 terminal 4 of constant current applying mode
Analytech Co., Ltd. manufactures：MCP-T610 types) measure etching before and after film resistance value.Calculated according to the change of the resistance value
Go out Thickness Variation, calculate etch-rate.
Cone angle is measured as described below.First, on the glass substrate by sputtering method with 20nm thickness by molybdenum into
Film, continue that copper film forming is made to Cu/Mo multilayer membrane sample with 300nm thickness thereon.Pattern shape is formed on the copper film
As the protective agent of wiring shape, the base material of formation cone angle evaluation.That is, base material is by substrate, molybdenum film, copper film and copper film thereon
On by pattern formed protection oxidant layer form.The time for making the base material appropriately be etched is impregnated in etching solution, carries out
Etching.Sample after cleaning etching simultaneously makes its drying, then cuts off wiring portion, section is cut in observation.
The observation for cutting section uses SEM (Hitachi, Ltd.'s manufactures：SU8020 types) accelerating potential 1kV, 30000~
Carried out under conditions of 50000 times.Start time untill film transmitted light it should be noted that appropriate etching is self etching.With
At the time of visually confirming film transmitted light.
Cross sectional shape will be cut and be shown in Fig. 1.As shown in Fig. 1 (a), by formed by substrate 1 and the inclined plane 6 being etched
Angle 5 is as cone angle (°).If cone angle 5 is 30~60 °, it is judged as circle (zero).Outside if the scope of the angle, then sentence
Break to pitch (×).It should be noted that " circle " refers to successfully or qualified, " fork " refers to failure or unqualified.Following evaluation
It is identical.It should be noted that in Fig. 1 (a), Mo layers symbol 3 represents, Cu layers symbol 2 represents, the protective agent table of symbol 4
Show.
The undercutting of molybdenum layer refers to as shown in the symbol 10 of Fig. 1 (b), by fast-etching between molybdenum layer 3 and substrate 1
State (back taper).Evaluation can be carried out simultaneously in the evaluation of cone angle 5.Undercutting for molybdenum layer, if the 30000 of SEM
It is undiscovered into 50000 times of observation again, it is judged as circle (zero), is judged as pitching (×) if being found.
For Mo residues, in the observation using light microscope and SEM, if it is confirmed that being then judged to pitching to residue
(×), it is determined as circle (zero) if residue is not confirmed.It should be noted that times of the light microscope at 100 times or so
Observed under rate, with bright-field observation and dark field.In addition, in SEM, observed with 30000 times to 50000 times.
Overetch patience (also referred to as " O.E. patience ") refers to, observes with 2 times of the time of the time needed for appropriate etch
The undercutting of cone angle, molybdenum layer when being etched, Mo residues, it is judged as circle (zero) if all being evaluated as " justifying ".If any 1
It is individual be evaluated as " pitching " be then judged as pitch (×).
For the presence or absence of precipitate, after allocating etching solution, room temperature places the stipulated time (3 hours) in bottle in advance, with mesh
Depending on judging precipitate azury whether is produced in bottle.In the case of producing precipitate, with filter paper filtered etch liquid, make on filter paper
The foreign matter of residual carries out pure water cleaning, drying at room temperature, utilizes the FT-IR (IR of Shimadzu Scisakusho Ltd's manufacture
Affinity), SEM-EDX (HORIBA, Ltd are manufactured) analysis gained crystal thing, powder.If precipitate is not by visual observation
To circle (zero) is then judged as, situation about visually being confirmed is judged as pitching (×).
For etching solution, it is important that do not produce the aspect of precipitate and the cross sectional shape of wiring is adapted to, for extension slot
Liquid life-span, the decomposition rate of hydrogen peroxide are also changed into important project.It is herein incorporated by reference, hydrogen peroxide decomposition rate also serves as
Assessment item is investigated.
Hydrogen peroxide decomposition rate is carried out as follows measure：Using potassium permanganate as titer reagent, automatic titration device is used
The GT-200 of manufacture (Mitsubishi Chemical Analytech Co., Ltd.s), determine after etching solution is just allocated and
At 35 DEG C after the stipulated time (about 24 hours) concentration of hydrogen peroxide.Then, according to the variable quantity of concentration of hydrogen peroxide
Calculate decomposition rate (quality %/day).The decomposition rate of concentration of hydrogen peroxide below 1 mass %/day if then thinking measuring
Had no problem in production scale.
(embodiment 1)
Using comprising as acid organic acid
The mass % of glycolic 1.87,
The mass % of malonic acid 3.41,
The mass % of lactic acid 0.69,
As amines
The mass % of 1- amino -2- propyl alcohol 2.20,
As water stabilizer excessively
The mass % of phenylurea 0.10,
As azole
1H-TETRAZOLE -5- amine monohydrates (CH3N5·H2O：It is same as below) 0.12 mass %
As anti-precipitation agent
The mass % of aluminum nitrate 0.28
Etching solution raw material and the mass % of water 86.03 allocate, prepare etching concentrate.It should be noted that herein, water
Include the water of hydrogen peroxide as described below.It is also identical in following embodiment and comparative example.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And copper sulphate is added, with copper ion concentration (for " Cu concentration " described in table.It is same as below.) mode that reaches 2000ppm carries out
Prepare.In addition, molybdenum trisulfate is added, with molybdenum concentration (for " Mo concentration " described in table.It is same as below.) mode that reaches 200ppm enters
It is prepared by row.In addition, liquid temperature uses at 35 DEG C.The result that each composition is accounted for the overall concentration of etching solution and each evaluation item is shown in
Table 1.
(embodiment 2)
Using comprising as acid organic acid
The mass % of glycolic 1.87,
The mass % of malonic acid 3.41,
The mass % of lactic acid 0.69,
As amines
The mass % of 1- amino -2- propyl alcohol 2.20,
As water stabilizer excessively
The mass % of phenylurea 0.10,
As azole
The mass % of 1H-TETRAZOLE -5- amine monohydrate 0.12
As anti-precipitation agent
The mass % of aluctyl 0.22
Etching solution raw material and the mass % of water 86.09 allocate, prepare etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And copper sulphate is added, prepared in a manner of copper ion concentration reaches 2000ppm.In addition, molybdenum trisulfate is added, with molybdenum concentration
It is prepared by the mode for reaching 200ppm.In addition, liquid temperature uses at 35 DEG C.Each composition is accounted for into the overall concentration of etching solution and each
The result of evaluation item is shown in table 1.
(embodiment 3)
As comprising as acid organic acid
The mass % of glycolic 1.87,
The mass % of malonic acid 3.41,
The mass % of lactic acid 0.69,
As amines
The mass % of 1- amino -2- propyl alcohol 2.20,
As water stabilizer excessively
The mass % of phenylurea 0.10,
As azole
The mass % of 1H-TETRAZOLE -5- amine monohydrate 0.12
As anti-precipitation agent
The mass % of Beta-alanine 0.56,
The mass % of aluminum nitrate 0.28
Etching solution raw material and the mass % of water 85.47 allocate, prepare etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And copper sulphate is added, prepared in a manner of copper ion concentration reaches 2000ppm.In addition, molybdenum trisulfate is added, with molybdenum concentration
It is prepared by the mode for reaching 200ppm.In addition, liquid temperature uses at 35 DEG C.Each composition is accounted for into the overall concentration of etching solution and each
The result of evaluation item is shown in table 1.
(embodiment 4)
Using comprising as acid organic acid
The mass % of glycolic 1.87,
The mass % of malonic acid 3.41,
The mass % of lactic acid 0.69,
As amines
The mass % of 1- amino -2- propyl alcohol 2.20,
As water stabilizer excessively
The mass % of phenylurea 0.10,
As azole
The mass % of 1H-TETRAZOLE -5- amine monohydrate 0.12
As anti-precipitation agent
The mass % of Beta-alanine 0.56,
The mass % of aluctyl 0.22
Etching solution raw material and the mass % of water 85.53 allocate, prepare etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And copper sulphate is added, prepared in a manner of copper ion concentration reaches 2000ppm.In addition, molybdenum trisulfate is added, with molybdenum concentration
It is prepared by the mode for reaching 200ppm.In addition, liquid temperature uses at 35 DEG C.Each composition is accounted for into the overall concentration of etching solution and each
The result of evaluation item is shown in table 1.
(embodiment 5)
Using comprising as acid organic acid
The mass % of glycolic 1.87,
The mass % of malonic acid 3.41,
The mass % of lactic acid 0.08,
As amines
The mass % of 1- amino -2- propyl alcohol 2.20,
As water stabilizer excessively
The mass % of phenylurea 0.10,
As azole
The mass % of 1H-TETRAZOLE -5- amine monohydrate 0.12
As anti-precipitation agent
The mass % of Beta-alanine 0.56,
The mass % of aluctyl 0.87
Etching solution raw material and the mass % of water 85.49 allocate, prepare etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And copper sulphate is added, prepared in a manner of copper ion concentration reaches 2000ppm.In addition, molybdenum trisulfate is added, with molybdenum concentration
It is prepared by the mode for reaching 200ppm.In addition, liquid temperature uses at 35 DEG C.Each composition is accounted for into the overall concentration of etching solution and each
The result of evaluation item is shown in table 1.
(comparative example 1)
Using comprising as inorganic acid
The mass % of nitric acid 0.06,
As acid organic acid
The mass % of glycolic 1.87,
The mass % of malonic acid 3.42
The mass % of lactic acid 0.81
As amines
The mass % of 1- amino -2- propyl alcohol 2.28,
As water stabilizer excessively
The mass % of phenylurea 0.10,
As azole
The mass % of 1H-TETRAZOLE -5- amine monohydrate 0.12
Etching solution raw material and the mass % of water 86.04 allocate, prepare etching concentrate.Do not include in the comparative example 1 suitable
In the material of anti-precipitation agent.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And copper sulphate is added, prepared in a manner of copper ion concentration reaches 2000ppm.In addition, molybdenum trisulfate is added, with molybdenum concentration
It is prepared by the mode for reaching 200ppm.In addition, liquid temperature uses at 35 DEG C.Each composition is accounted for into the overall concentration of etching solution and each
The result of evaluation item is shown in table 2.
(comparative example 2)
Using comprising as acid organic acid
The mass % of glycolic 1.87,
The mass % of malonic acid 3.41
The mass % of lactic acid 0.87
As amines
The mass % of 1- amino -2- propyl alcohol 2.20,
As water stabilizer excessively
The mass % of phenylurea 0.10,
As azole
The mass % of 1H-TETRAZOLE -5- amine monohydrate 0.12
As anti-precipitation agent
The mass % of Beta-alanine 0.55 etching solution raw material is allocated with the mass % of water 85.58, prepares etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And copper sulphate is added, prepared in a manner of copper ion concentration reaches 2000ppm.In addition, molybdenum trisulfate is added, with molybdenum concentration
It is prepared by the mode for reaching 200ppm.In addition, liquid temperature uses at 35 DEG C.Each composition is accounted for into the overall concentration of etching solution and each
The result of evaluation item is shown in table 2.
(comparative example 3)
Using comprising as acid organic acid
The mass % of glycolic 1.87,
The mass % of malonic acid 3.41
The mass % of lactic acid 0.87
As amines
The mass % of 1- amino -2- propyl alcohol 2.20,
As water stabilizer excessively
The mass % of phenylurea 0.10,
As azole
The mass % of 1H-TETRAZOLE -5- amine monohydrate 0.12
As anti-precipitation agent
The mass % of glycine 0.55 etching solution raw material is allocated with the mass % of water 85.58, prepares etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And copper sulphate is added, prepared in a manner of copper ion concentration reaches 2000ppm.In addition, molybdenum trisulfate is added, with molybdenum concentration
It is prepared by the mode for reaching 200ppm.In addition, liquid temperature uses at 35 DEG C.Each composition is accounted for into the overall concentration of etching solution and each
The result of evaluation item is shown in table 2.
(comparative example 4)
Using comprising as acid organic acid
The mass % of glycolic 1.87,
The mass % of malonic acid 3.41
The mass % of lactic acid 0.87
As amines
The mass % of 1- amino -2- propyl alcohol 2.20,
As water stabilizer excessively
The mass % of phenylurea 0.10,
As azole
The mass % of 1H-TETRAZOLE -5- amine monohydrate 0.12
As anti-precipitation agent
The mass % of EDTA (ethylenediamine tetra-acetic acid) 0.55 etching solution raw material is allocated with the mass % of water 85.58, prepares etching
Concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And copper sulphate is added, prepared in a manner of copper ion concentration reaches 2000ppm.In addition, molybdenum trisulfate is added, with molybdenum concentration
It is prepared by the mode for reaching 200ppm.In addition, liquid temperature uses at 35 DEG C.Each composition is accounted for into the overall concentration of etching solution and each
The result of evaluation item is shown in table 2.
(comparative example 5)
Want to make and include as acid organic acid
The mass % of glycolic 1.87,
The mass % of malonic acid 3.41
The mass % of lactic acid 0.69
As amines
The mass % of 1- amino -2- propyl alcohol 2.20,
As water stabilizer excessively
The mass % of phenylurea 0.10,
As azole
The mass % of 1H-TETRAZOLE -5- amine monohydrate 0.12
As anti-precipitation agent
The etching solution raw material of aluminium hydroxide, but aluminium hydroxide does not dissolve, and can not make etching solution raw material.Show the result in table
3。
(comparative example 6)
Using comprising as acid organic acid
The mass % of glycolic 1.87,
The mass % of malonic acid 3.41
The mass % of lactic acid 0.69
As amines
The mass % of 1- amino -2- propyl alcohol 2.20,
As water stabilizer excessively
The mass % of phenylurea 0.10,
As azole
The mass % of 1H-TETRAZOLE -5- amine monohydrate 0.12
As anti-precipitation agent
The mass % of nickel sulfate 0.38 etching solution raw material is allocated with the mass % of water 91.23, prepares etching concentrate.
35% hydrogen peroxide and etching concentrate are mixed, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And copper sulphate is added, prepared in a manner of copper ion concentration reaches 2000ppm.In addition, molybdenum trisulfate is added, with molybdenum concentration
It is prepared by the mode for reaching 200ppm.In addition, liquid temperature uses at 35 DEG C.Each composition is accounted for into the overall concentration of etching solution and each
The result of evaluation item is shown in table 3.
(comparative example 7)
Using comprising as oxidant
Copper sulphate (CuSO4) 1.35 mass %,
As acid organic acid
The mass % of citric acid 10.00,
The mass % of glycine 15.00
Etching solution raw material and the mass % of water 75.00 allocate, prepare etching solution.
And then copper sulphate is added, prepared in a manner of copper ion concentration reaches 5000ppm.In addition, liquid temperature is at 30 DEG C
Lower use.The result that each composition is accounted for the overall concentration of etching solution and each evaluation item is shown in table 4.
(comparative example 8)
Using comprising as oxidant
Copper sulphate (CuSO4) 5.88 mass %,
As acid organic acid
The mass % of citric acid 10.00,
The mass % of glycine 15.00
Etching solution raw material and the mass % of water 75.00 allocate, prepare etching solution.
And then copper sulphate is added, prepared in a manner of copper ion concentration reaches 24000ppm.In addition, liquid temperature is 30
Used at DEG C.The result that each composition is accounted for the overall concentration of etching solution and each evaluation item is shown in table 4.
(comparative example 9)
Using comprising as oxidant
Copper chloride (CuCl2) 1.10 mass %,
As acid organic acid
The mass % of citric acid 10.00,
The mass % of glycine 15.00
Etching solution raw material and the mass % of water 73.90 allocate, prepare etching solution.
And then stannous chloride is added, prepared in a manner of copper ion concentration reaches 5000ppm.In addition, liquid temperature is 30
Used at DEG C.The result that each composition is accounted for the overall concentration of etching solution and each evaluation item is shown in table 4.
(comparative example 10)
Using comprising as oxidant
Copper chloride (CuCl2) 5.10 mass %,
As acid organic acid
The mass % of citric acid 10.00,
The mass % of glycine 15.00
Etching solution raw material and the mass % of water 69.90 allocate, prepare etching solution.
And then stannous chloride is added, prepared in a manner of copper ion concentration reaches 24000ppm.In addition, liquid temperature exists
Used at 30 DEG C.The result that each composition is accounted for the overall concentration of etching solution and each evaluation item is shown in table 4.
(comparative example 11)
Using comprising as oxidant
Copper chloride (CuCl2) 1.20 mass %,
As acid organic acid
The mass % of citric acid 10.00,
The mass % of Beta-alanine 15.00
Etching solution raw material and the mass % of water 73.80 allocate, prepare etching solution.
And then stannous chloride is added, prepared in a manner of copper ion concentration reaches 5000ppm.In addition, liquid temperature is 30
Used at DEG C.The result that each composition is accounted for the overall concentration of etching solution and each evaluation item is shown in table 4.
(comparative example 12)
Using comprising as oxidant
Copper chloride (CuCl2) 5.00 mass %,
As acid organic acid
The mass % of citric acid 10.00,
The mass % of Beta-alanine 15.00
Etching solution raw material and the mass % of water 70.00 allocate, prepare etching solution.
And then stannous chloride is added, prepared in a manner of copper ion concentration reaches 24000ppm.In addition, liquid temperature exists
Used at 30 DEG C.The result that each composition is accounted for the overall concentration of etching solution and each evaluation item is shown in table 4.
[table 1]
[table 2]
[table 3]
[table 4]
＜ results ＞
Multilayer film etching solution of the embodiment 1 to embodiment 5 for the present invention.Due to therefore light blue without producing comprising aluminium salt
The precipitate (cupric oxalate) of color.In addition, when using Beta-alanine (embodiment 3 to 5) as neutral organic acid simultaneously with aluminium salt,
Unfavorable condition is not produced especially.In addition, acid organic acid is simultaneously using glycolic, malonic acid, this 3 kinds of lactic acid.They institute
Having does not have precipitate in sample, and cone angle, Mo undercutting, the project of Mo residues, O.E. patience are also round evaluation.And then
Hydrogen peroxide decomposition rate can obtain desired result again smaller than 0.1 mass %/day.
In addition, overetch patience is good, therefore, the time spent from appropriate etching can be with untill 2 times of time
It is etched with maintaining good cone angle.In addition, for the etching solution of these embodiments, even if Mo and Cu Film Thickness Ratio (t0/
T1 it is) different from the situation (20/300) of embodiment, 30 ° to 60 ° of cone can be realized if Film Thickness Ratio is between 0.01 to 0.2
Degree.
Comparative example 1 to comparative example 4 is by adding organic acid, complexing agent so as to having attempted the example of the seizure of copper ion.
Expect that it suppresses the reaction of copper ion and oxalic acid.Comparative example 1 is the situation of not aluminium containing salt.As composition, patent document is contained in
4.In comparative example 1, the reaction of oxalic acid and copper can not be suppressed, therefore generate cupric oxalate and produce precipitate.
In addition, the example of the effect for the Beta-alanine that comparative example 2 uses for investigation as the anti-precipitation agent of embodiment 3 to 5.
When aluminium salt is used together, suppress the generation of cupric oxalate, but when Beta-alanine is independent, the generation of cupric oxalate can not be suppressed.Thus
Understand, in embodiment each sample, suppress the generation of cupric oxalate by aluminium salt.
Comparative example 2 to 4 is the example that glycine, EDTA are added as anti-precipitation agent.Particularly, EDTA as complexing agent and
It is known, the preferential complexing of copper can be expected to suppress the effect of the generation of cupric oxalate.However, Beta-alanine, glycine,
EDTA can not suppress to separate out.In addition, their addition can produce Mo residues.That is, there is the etching for suppressing Mo.
Comparative example 5 and 6 is 1 research of aluminium salt species.In comparative example 5, aluminium salt is used as using aluminium hydroxide.However, hydrogen
Aluminum oxide, which can not be even dissolved in the etching solution, can not make etching solution.Comparative example 6 is to be tasted as the metallic element beyond aluminium
The result of nickel is tried.As anti-precipitation agent, nickel sulfate is used.However, for nickel sulfate, the generation of cupric oxalate can not be suppressed.
Comparative example 7 to 12 is the result for the example for having attempted the copper etchant solution without using hydrogen peroxide.Etching solution by oxidant,
Acid organic acid and water are formed.In comparative example 7 and 8, as oxidant, copper sulphate is used.In addition, in comparative example 9 to 12, use
Stannous chloride.In comparative example 7 to 12, the state using the copper concentration in etching solution as up to 5000 or 24000ppm is etched.
By the concentration for adjusting oxidant and organic acid, thus it is possible to vary the etch-rate of copper.However, molybdenum can not lose completely
Carve.On the other hand, due to without hydrogen peroxide, malonic acid, ethanol acids, therefore, the precipitate completely without cupric oxalate.Such as with
On, the etching solution of the copper based on oxidant and organic acid can be etched to copper, but be changed into the feelings of this 2 Rotating fields of molybdenum and copper
Under condition, as etching solution, it can not use.
Industrial applicability
The etching solution of the present invention no matter the FPD such as liquid crystal display, plasma scope, organic EL based article, make
It can also be utilized extensively with the situation for the wiring for being laminated with molybdenum layer and layers of copper.
Description of reference numerals
1 substrate
2 layers of copper
3 molybdenum layers
4 protective agents (layer)
5 cone angles
6 inclined planes
10 bottom cutting portions
Claims (10)
1. a kind of multilayer film etching solution comprising molybdenum and copper, it is characterised in that contain：
The mass % of 4.0 mass % of etching solution total amount~5.8 hydrogen peroxide,
The mass % of 1 mass % of etching solution total amount~7 acid organic acid,
The mass % of 0.5 mass % of etching solution total amount~2.0 amines,
The mass % of 0.5 mass % of etching solution total amount~2.0 hydrogen peroxide decomposing inhibitor,
Azole and
Anti- precipitation agent comprising aluminium salt,
The acid organic acid using formic acid, acetic acid, propionic acid, lactic acid, glycolic, diglycolic acid, pyruvic acid, malonic acid, butyric acid,
Hydroxybutyric acid, tartaric acid, butanedioic acid, malic acid, maleic acid, fumaric acid, valeric acid, glutaric acid, itaconic acid, caproic acid, adipic acid, lemon
Lemon acid, tricarballylic acid, trans-aconitic acid, enanthic acid, octanoic acid, laurate, myristic acid, palmitic acid, stearic acid, oleic acid, sub- oil
Acid, leukotrienes, benzoic acid, salicylic acid, mandelic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), carbamic acid, the third ammonia
Acid, glycine, asparagine, aspartic acid, methyl amimoacetic acid, serine, glutamine, glutamic acid, 4-Aminobutanoicacid, imino-diacetic
At least one of butyric acid, arginine, leucine, isoleucine, nitrilotriacetic acid,
Following compounds or a variety of following compounds of combination are used alone to use in the amines：Ethylenediamine, trimethylene
Diamines, 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- diaminobutanes, five methylene diamine, 2,4- 1,5-DAPs, hexa-methylene two
Amine, heptamethylene diamines, eight methylene diamines, nine methylene diamines, N- methyl ethylenediamines, N, N- dimethyl-ethylenediamines, front three
Base ethylenediamine, NEED, N, N- diethyl ethylenediamines, triethylethylenediamine, 1,2,3- triaminopropanes, hydrazine, three (2-
Amino-ethyl) amine, four (amino methyl) methane, diethylenetriamines, trien, tetren, seven ethylidene
Eight amine, the amine of nine ethylidene ten, diazabicylo endecatylene, monoethanolamine, N- methylethanolamines, N methyldiethanol amine, N- second
Ethylethanolamine, N- amino ethyl ethanolamines, 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-
Amino-propan -1- alcohol, N- ethyl -2- amino-propan -1- alcohol, 1- aminopropane -3- alcohol, N- methyl isophthalic acids-aminopropane -3-
Alcohol, N- ethyl -1- aminopropane -3- alcohol, 1- butylamine -2- alcohol, N- methyl isophthalic acids-butylamine -2- alcohol, N- ethyl -1- ammonia
Base butane -2- alcohol, 2- butylamine -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- methylpropane -1- alcohol, 1- aminopentane -4- alcohol, 2- amino -4- methylpentane -1- alcohol, 2- aminohexane -1- alcohol, 3- amino
Heptane -4- alcohol, 1- amino-octane -2- alcohol, 5- amino-octane -4- alcohol, 1- aminopropane -2,3- glycol, 2- aminopropanes -1,3-
Glycol, three (methylol) aminomethanes, 1,2- diaminopropanes -3- alcohol, 1,3- diaminopropanes -2- alcohol, 2- (2- amino ethoxies
Base) ethanol, 2- (2- aminoethylaminos) ethanol or diglycolamine,
The hydrogen peroxide decomposing inhibitor includes phenylurea, allylurea, 1,3- dimethyl ureas, thiocarbamide, phenyl acetamide, phenyl
At least one of ethylene glycol, 1- propyl alcohol or 2- propyl alcohol,
The azole include 1H- BTAs, 5- methyl isophthalic acid H- BTAs, 3- amino -1H- triazoles, 1H-TETRAZOLE, 5- methyl -
1H-TETRAZOLE, 5- phenyl -1H-TETRAZOLE, 5- amino -1H-TETRAZOLE, 1H- imidazoles, 1H- benzimidazoles, 1,3- thiazoles or 4- methyl thiazoliums
At least one of azoles,
The anti-precipitation agent comprising aluminium salt be aluminum sulfate, aluminum nitrate, aluminium chloride, aluctyl, aluminium acetate or aluminium carbonate in extremely
Few one kind.
2. the multilayer film etching solution according to claim 1 comprising molybdenum and copper, it is characterised in that the aluminium salt includes breast
Any one of sour aluminium or aluminum nitrate.
3. the multilayer film etching solution according to claim 1 comprising molybdenum and copper, it is characterised in that the acid organic acid
Comprising at least one kind of in glycolic, malonic acid, lactic acid.
4. the multilayer film etching solution according to claim 1 comprising molybdenum and copper, it is characterised in that the amines is
1- amino -2- propyl alcohol.
5. the multilayer film etching solution according to claim 1 comprising molybdenum and copper, it is characterised in that the hydrogen peroxide point
Solution inhibitor is phenylurea.
6. the multilayer film etching solution according to claim 1 comprising molybdenum and copper, it is characterised in that the azole is 1H-
Tetrazolium -5- amine.
7. the multilayer film etching solution according to claim 1 comprising molybdenum and copper, it is characterised in that in the anti-precipitation agent
Include Beta-alanine.
8. the multilayer film etching solution according to claim 1 comprising molybdenum and copper, it is characterised in that also comprising 500~
7000ppm copper ion.
9. a kind of multilayer film etching concentrate, it is characterised in that the multilayer film includes molybdenum and copper, and the etching concentrate contains
Have：
When being deployed into etching solution for etching solution total amount the mass % of 1 mass %~7 acid organic acid,
When being deployed into etching solution for etching solution total amount the mass % of 0.5 mass %~2.0 amines,
When being deployed into etching solution for etching solution total amount the mass % of 0.5 mass %~2.0 hydrogen peroxide decomposing inhibitor,
Azole,
Anti- precipitation agent comprising aluminium salt and
Water,
The acid organic acid using formic acid, acetic acid, propionic acid, lactic acid, glycolic, diglycolic acid, pyruvic acid, malonic acid, butyric acid,
Hydroxybutyric acid, tartaric acid, butanedioic acid, malic acid, maleic acid, fumaric acid, valeric acid, glutaric acid, itaconic acid, caproic acid, adipic acid, lemon
Lemon acid, tricarballylic acid, trans-aconitic acid, enanthic acid, octanoic acid, laurate, myristic acid, palmitic acid, stearic acid, oleic acid, sub- oil
Acid, leukotrienes, benzoic acid, salicylic acid, mandelic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), carbamic acid, the third ammonia
Acid, glycine, asparagine, aspartic acid, methyl amimoacetic acid, serine, glutamine, glutamic acid, 4-Aminobutanoicacid, imino-diacetic
At least one of butyric acid, arginine, leucine, isoleucine, nitrilotriacetic acid,
Following compounds or a variety of following compounds of combination are used alone to use in the amines：Ethylenediamine, trimethylene
Diamines, 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- diaminobutanes, five methylene diamine, 2,4- 1,5-DAPs, hexa-methylene two
Amine, heptamethylene diamines, eight methylene diamines, nine methylene diamines, N- methyl ethylenediamines, N, N- dimethyl-ethylenediamines, front three
Base ethylenediamine, NEED, N, N- diethyl ethylenediamines, triethylethylenediamine, 1,2,3- triaminopropanes, hydrazine, three (2-
Amino-ethyl) amine, four (amino methyl) methane, diethylenetriamines, trien, tetren, seven ethylidene
Eight amine, the amine of nine ethylidene ten, diazabicylo endecatylene, monoethanolamine, N- methylethanolamines, N methyldiethanol amine, N- second
Ethylethanolamine, N- amino ethyl ethanolamines, 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-
Amino-propan -1- alcohol, N- ethyl -2- amino-propan -1- alcohol, 1- aminopropane -3- alcohol, N- methyl isophthalic acids-aminopropane -3-
Alcohol, N- ethyl -1- aminopropane -3- alcohol, 1- butylamine -2- alcohol, N- methyl isophthalic acids-butylamine -2- alcohol, N- ethyl -1- ammonia
Base butane -2- alcohol, 2- butylamine -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- methylpropane -1- alcohol, 1- aminopentane -4- alcohol, 2- amino -4- methylpentane -1- alcohol, 2- aminohexane -1- alcohol, 3- amino
Heptane -4- alcohol, 1- amino-octane -2- alcohol, 5- amino-octane -4- alcohol, 1- aminopropane -2,3- glycol, 2- aminopropanes -1,3-
Glycol, three (methylol) aminomethanes, 1,2- diaminopropanes -3- alcohol, 1,3- diaminopropanes -2- alcohol, 2- (2- amino ethoxies
Base) ethanol, 2- (2- aminoethylaminos) ethanol or diglycolamine,
The hydrogen peroxide decomposing inhibitor includes phenylurea, allylurea, 1,3- dimethyl ureas, thiocarbamide, phenyl acetamide, phenyl
At least one of ethylene glycol, 1- propyl alcohol or 2- propyl alcohol,
The azole include 1H- BTAs, 5- methyl isophthalic acid H- BTAs, 3- amino -1H- triazoles, 1H-TETRAZOLE, 5- methyl -
1H-TETRAZOLE, 5- phenyl -1H-TETRAZOLE, 5- amino -1H-TETRAZOLE, 1H- imidazoles, 1H- benzimidazoles, 1,3- thiazoles or 4- methyl thiazoliums
At least one of azoles,
The anti-precipitation agent comprising aluminium salt be aluminum sulfate, aluminum nitrate, aluminium chloride, aluctyl, aluminium acetate or aluminium carbonate in extremely
Few one kind.
10. a kind of multilayer film engraving method comprising molybdenum and copper, it is characterised in that including following process：
Allotment etching concentrate, water and when being deployed into etching solution for etching solution total amount the mass % of 4.0 mass %~5.8 peroxide
Change hydrogen, so as to allocate the process of multilayer film etching solution,
The etching concentrate contains：When being deployed into etching solution for etching solution total amount the mass % of 1 mass %~7 it is acid organic
Acid,
When being deployed into etching solution for etching solution total amount the mass % of 0.5 mass %~2.0 amines,
When being deployed into etching solution for etching solution total amount the mass % of 0.5 mass %~2.0 hydrogen peroxide decomposing inhibitor,
Azole,
Anti- precipitation agent comprising aluminium salt and
Water；And
The process for making the multilayer film etching solution be contacted with processed substrate,
The acid organic acid using formic acid, acetic acid, propionic acid, lactic acid, glycolic, diglycolic acid, pyruvic acid, malonic acid, butyric acid,
Hydroxybutyric acid, tartaric acid, butanedioic acid, malic acid, maleic acid, fumaric acid, valeric acid, glutaric acid, itaconic acid, caproic acid, adipic acid, lemon
Lemon acid, tricarballylic acid, trans-aconitic acid, enanthic acid, octanoic acid, laurate, myristic acid, palmitic acid, stearic acid, oleic acid, sub- oil
Acid, leukotrienes, benzoic acid, salicylic acid, mandelic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), carbamic acid, the third ammonia
Acid, glycine, asparagine, aspartic acid, methyl amimoacetic acid, serine, glutamine, glutamic acid, 4-Aminobutanoicacid, imino-diacetic
At least one of butyric acid, arginine, leucine, isoleucine, nitrilotriacetic acid,
Following compounds or a variety of following compounds of combination are used alone to use in the amines：Ethylenediamine, trimethylene
Diamines, 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- diaminobutanes, five methylene diamine, 2,4- 1,5-DAPs, hexa-methylene two
Amine, heptamethylene diamines, eight methylene diamines, nine methylene diamines, N- methyl ethylenediamines, N, N- dimethyl-ethylenediamines, front three
Base ethylenediamine, NEED, N, N- diethyl ethylenediamines, triethylethylenediamine, 1,2,3- triaminopropanes, hydrazine, three (2-
Amino-ethyl) amine, four (amino methyl) methane, diethylenetriamines, trien, tetren, seven ethylidene
Eight amine, the amine of nine ethylidene ten, diazabicylo endecatylene, monoethanolamine, N- methylethanolamines, N methyldiethanol amine, N- second
Ethylethanolamine, N- amino ethyl ethanolamines, 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-
Amino-propan -1- alcohol, N- ethyl -2- amino-propan -1- alcohol, 1- aminopropane -3- alcohol, N- methyl isophthalic acids-aminopropane -3-
Alcohol, N- ethyl -1- aminopropane -3- alcohol, 1- butylamine -2- alcohol, N- methyl isophthalic acids-butylamine -2- alcohol, N- ethyl -1- ammonia
Base butane -2- alcohol, 2- butylamine -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- methylpropane -1- alcohol, 1- aminopentane -4- alcohol, 2- amino -4- methylpentane -1- alcohol, 2- aminohexane -1- alcohol, 3- amino
Heptane -4- alcohol, 1- amino-octane -2- alcohol, 5- amino-octane -4- alcohol, 1- aminopropane -2,3- glycol, 2- aminopropanes -1,3-
Glycol, three (methylol) aminomethanes, 1,2- diaminopropanes -3- alcohol, 1,3- diaminopropanes -2- alcohol, 2- (2- amino ethoxies
Base) ethanol, 2- (2- aminoethylaminos) ethanol or diglycolamine,
The hydrogen peroxide decomposing inhibitor includes phenylurea, allylurea, 1,3- dimethyl ureas, thiocarbamide, phenyl acetamide, phenyl
At least one of ethylene glycol, 1- propyl alcohol or 2- propyl alcohol,
The azole include 1H- BTAs, 5- methyl isophthalic acid H- BTAs, 3- amino -1H- triazoles, 1H-TETRAZOLE, 5- methyl -
1H-TETRAZOLE, 5- phenyl -1H-TETRAZOLE, 5- amino -1H-TETRAZOLE, 1H- imidazoles, 1H- benzimidazoles, 1,3- thiazoles or 4- methyl thiazoliums
At least one of azoles,
The anti-precipitation agent comprising aluminium salt be aluminum sulfate, aluminum nitrate, aluminium chloride, aluctyl, aluminium acetate or aluminium carbonate in extremely
Few one kind,
The multilayer film etching solution and the process that processed substrate contacts is set in the pH of the multilayer film etching solution to be 2 to 6
Scope and liquid temperature be 20 DEG C to 40 DEG C under conditions of carry out.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014091779A JP5866566B2 (en) | 2014-04-25 | 2014-04-25 | Etching solution, etching concentrate and etching method for multilayer film containing molybdenum and copper |
| JP2014-091779 | 2014-04-25 | ||
| PCT/JP2015/002216 WO2015162934A1 (en) | 2014-04-25 | 2015-04-24 | Etching solution for multi-layer film containing molybdenum and copper, etching concentrate, and etching method |
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| CN106255777A CN106255777A (en) | 2016-12-21 |
| CN106255777B true CN106255777B (en) | 2018-03-20 |
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Country Status (4)
| Country | Link |
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| JP (1) | JP5866566B2 (en) |
| CN (1) | CN106255777B (en) |
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| JP6494254B2 (en) | 2014-11-18 | 2019-04-03 | 関東化學株式会社 | Copper / molybdenum metal laminated film etching solution composition, etching method using the composition, and method for extending the life of the composition |
| TWI706056B (en) * | 2015-12-21 | 2020-10-01 | 日商三菱瓦斯化學股份有限公司 | Liquid composition for etching a multilayer film containing copper and molybdenum, etching method using the liquid composition, and manufacturing method of display device |
| TWI618817B (en) * | 2015-12-29 | 2018-03-21 | Daxin Materials Corporation | Etchant composition and etching method using thereof |
| CN105862040A (en) | 2016-06-20 | 2016-08-17 | 深圳市华星光电技术有限公司 | Copper-etching solution additive and production method of copper-etching solution |
| JP6167444B1 (en) * | 2016-09-09 | 2017-07-26 | パナソニックＩｐマネジメント株式会社 | Etching solution for multilayer film, etching concentrated solution, and etching method |
| WO2018116991A1 (en) * | 2016-12-21 | 2018-06-28 | 東洋製罐グループホールディングス株式会社 | Method for decomposing polyoxalate |
| 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 |
| KR20190027019A (en) * | 2017-09-04 | 2019-03-14 | 삼성디스플레이 주식회사 | Etchant and fabrication method of metal pattern and thin film transistor substrate using the same |
| CN109415818A (en) * | 2018-03-23 | 2019-03-01 | 松下知识产权经营株式会社 | Copper thick film etching solution |
| 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 |
| CN110219003B (en) * | 2019-07-01 | 2021-08-24 | 江苏和达电子科技有限公司 | Etching solution for etching metal layer composed of copper layer and molybdenum layer and application thereof |
| CN110923713B (en) * | 2019-12-31 | 2020-12-08 | 成都中电熊猫显示科技有限公司 | Etching liquid for copper-molybdenum and alloy films and preparation method thereof |
| CN111809182A (en) * | 2020-07-08 | 2020-10-23 | 江苏和达电子科技有限公司 | Etching liquid for copper/molybdenum (niobium)/IGZO film layer and preparation method and application thereof |
| CN116240547B (en) * | 2022-12-25 | 2024-03-12 | 湖北兴福电子材料股份有限公司 | Copper etching solution and preparation method thereof |
| CN116103655A (en) * | 2022-12-25 | 2023-05-12 | 江苏中德电子材料科技有限公司 | Metal alkaline etching solution for integrated circuit and preparation method thereof |
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| CN1510169A (en) * | 2002-12-12 | 2004-07-07 | Lg.菲利浦Lcd株式会社 | Etching solution for multi-layer copper and molybdenum and etching method therewith |
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| CN1510169A (en) * | 2002-12-12 | 2004-07-07 | Lg.菲利浦Lcd株式会社 | Etching solution for multi-layer copper and molybdenum and etching method therewith |
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| JP5866566B2 (en) | 2016-02-17 |
| JP2015209568A (en) | 2015-11-24 |
| WO2015162934A1 (en) | 2015-10-29 |
| CN106255777A (en) | 2016-12-21 |
| TW201606135A (en) | 2016-02-16 |
| TWI560318B (en) | 2016-12-01 |
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