CN106255777A - Comprise the multilayer film etching solution of molybdenum and copper, etching concentrated solution and engraving method - Google Patents
Comprise the multilayer film etching solution of molybdenum and copper, etching concentrated solution and engraving method Download PDFInfo
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- CN106255777A CN106255777A CN201580021009.3A CN201580021009A CN106255777A CN 106255777 A CN106255777 A CN 106255777A CN 201580021009 A CN201580021009 A CN 201580021009A CN 106255777 A CN106255777 A CN 106255777A
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- etching solution
- copper
- acid
- molybdenum
- multilayer film
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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
Abstract
In the etching solution utilizing a kind of liquid that the multilayer film of molybdenum and copper is etched, it is desirable in crossing water, mixed organic acid uses.But, cross water and make organic acid oxidation decompose and generate oxalic acid, therefore there is the problem of the precipitate producing a large amount of cupric oxalate in etching solution.The multilayer film etching solution comprising molybdenum and copper is combined with oxalic acid by aluminium ion thus suppresses the generation of cupric oxalate, therefore, etching solution will not produce precipitate, the described multilayer film etching solution comprising molybdenum and copper is characterised by, contains: hydrogen peroxide, acid organic acid, amines, hydrogen peroxide decomposing inhibitor, azole and the anti-precipitation agent comprising aluminium salt.And, the cross sectional shape at the edge after etching can form the most positive cone-shaped.
Description
Technical field
The present invention relates to copper and the multilamellar of molybdenum used in the wiring purposes of the flat faced display to liquid crystal, organic EL etc.
That use when film is etched, multilayer film etching solution and etching concentrated solution and engraving method.
Background technology
Flat faced display (FPD) for liquid crystal, organic EL (electroluminescent, Electro-Luminescence) etc.
TFT (thin film transistor (TFT), Thin Film Transistor), employs aluminum as wiring material.In recent years, big picture and high-precision
The FPD of fineness popularizes, it is desirable to the wiring material used is the material that resistance ratio aluminum is low.Therefore, in recent years, resistance ratio is employed
The low copper of aluminum is as wiring material.
When using copper as wiring material, can produce and the bonding force between substrate and the diffusion to semiconductor substrate these 2
Problem.That is, in the case of using in grid wiring, even if using the sputtering method bigger to the collision energy of base material, there is also
The situation that bonding force is insufficient between the substrates such as glass.It addition, in the case of using in source/drain connects up, can produce
The problem that the copper of attachment spreads to the silicon as substrate, can change the electric design load of quasiconductor.
In order to solve this problem, have employed at present and form molybdenum film, the most thereon shape the most on a semiconductor substrate
Become the multiple structure of copper film.
Being routed through of FPD carries out wet etching to the multilayer film using sputtering method to be formed and is formed.This is because: due to
Can disposably large area be formed, therefore, it is possible to shorten operation.Herein, in the wet etching of wiring, it is important that with lower section
Face.
(1) machining accuracy is highly consistent.
(2) the wiring cross section after processing is the positive cone of predetermined angular.
(3) owing to comprising copper ion, therefore etch-rate will not change (bath life length).
(4) generation of precipitate is few.
Highly consistent as the machining accuracy of the 1st project is not only to carry out tiny area carrying out wet etching
Add the project necessarily required man-hour.As wiring being shaped as of cross section of the 2nd project, forming large-area FPD's in the lump
During wiring, the shape needed to carry out certain wiring to be formed.This is because, the etched limit of the multilayer film of copper and molybdenum
The part of edge can be when substrate is formed with the positive cone of 30～60 degree, even if generation etches the etch-rate of bad or copper and molybdenum
Balance difference, it is also possible to guarantee can ensure that the surplus of product quality.
3rd project is the problem of etching solution its shelf-life.In order to large-area substrate is etched, need substantial amounts of erosion
Carve liquid.These etching solutions can also recycle from the viewpoint of cost.It is able to maintain that the period (life-span) of its etching performance
The cost step-down of elder as far as possible is honest and clean.
It addition, the 4th project is not only the problem maintaining Etaching device, it it is also the problem of the quality problems being related to product.
When producing precipitate because of etching, it may occur that the pipe arrangement of Etaching device blocking or make the hole of spray nozzle of sprinkling etching solution block up
Plug.The reason that these phenomenons become Etaching device stopping is relevant with the rising of cost.It addition, precipitate adheres to by etching solution
Time on product, become short circuit, the reason of open circuit, the problem becoming the quality being directly connected to product.
About copper and the etching solution of the multilayer film of molybdenum, it was recently reported that containing in neutral salt and organic acid at least one and
The etching solution (patent documentation 1) of hydrogen peroxide.
It addition, report the etching solution of following copper molybdenum film: it contains with ormal weight respectively: hydrogen peroxide, organic acid, phosphorus
Hydrochlorate, the water solublity cyclic amine compound as the 1st additive, a kind of containing in amino and carboxyl as the 2nd additive
Water soluble compound, fluorine compounds and deionized water (patent documentation 2).
It addition, report the molybdenum/copper containing hydrogen peroxide, organic acid, three azole compounds, fluorine compounds and ultra-pure water/
Molybdenum nitride multiple film wiring etching solution (patent documentation 3).
Additionally, there was reported the plural layers etching solution comprising layers of copper and molybdenum layer as follows, it contains: (A) hydrogen peroxide；
(B) mineral acid without fluorine atom；(C) at least one in succinic acid, glycolic, lactic acid, malonic acid and malic acid has
Machine acid；(D) carbon number 2～10 and the amines that has in the way of they total group numbers are more than two of amino and hydroxyl；
(E) 5-amino-1H-TETRAZOLE；And (F) stabilizer of hydrogen peroxide, pH is 2.5～5 (patent documentations 4).
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2002-302780 publication (Japanese Patent No. 4282927)
Patent documentation 2: Japanese Unexamined Patent Publication 2004-193620 publication (Japanese Patent No. 4448322)
Patent documentation 3: Japanese Unexamined Patent Publication 2007-005790 publication (Japanese Patent No. 5111790)
Patent documentation 4: international publication number WO2011/099624 (Japanese Patent No. 5051323)
Summary of the invention
The problem that invention is to be solved
Patent documentation 1 only discloses in the case of the mixed liquor of hydrogen peroxide and organic acid, if regulation hydrogen peroxide
Ratio, then can make the content that the etch-rate of copper and molybdenum is etched in the same manner, entirely without open about concrete etching
The composition of liquid.
Patent documentation 2,3 uses fluorine compounds in the composition.Therefore, the most only glass substrate, silicon substrate also can be etched
Problem, also produce the environmental pressure when etching solution discarded and become big problem.
Patent documentation 4 have studied the etching of copper and molybdenum in detail.But, the composition of the etching solution of patent documentation 4 produces
A large amount of problems producing precipitate in etching solution.What particularly amount of precipitation was most is the precipitate being light blue color.It utilizes XRD (X
X ray diffraction analysis x device), FTIR (Fourier transform infrared spectroscopy device) confirm as cupric oxalate.
But, patent documentation 4 does not comprise oxalic acid.However the reason that cupric oxalate is considered following is still generated.?
Know that the oxidizing force of hydrogen peroxide is strong.The etching solution of patent documentation 4 comprises the organic acid such as malonic acid, glycolic.Hydrogen peroxide leads to
Cross and these organic acid are carried out oxidation Decomposition and generates oxalic acid.And think, this oxalic acid and the Cu in etching solution2+Ion forms network
Compound generates cupric oxalate.
Cupric oxalate is low due to dissolubility, the few Cu of the amount therefore generated by the oxidation Decomposition of organic acid2+Ion there is also
Time, positively become precipitate.On the other hand, comprise in the etching solution of hydrogen peroxide containing organic acid time, it is known to be suitable for
Adjustment is in the effect of the cone angle of the boundary member formation of etched copper film.Therefore, etching solution is comprising hydrogen peroxide and having
On the basis of machine acid, expectation can also suppress the composition of the generation of cupric oxalate.
For solving the scheme of problem
The present invention expects in view of above-mentioned problem, it is provided that: meet the wet method to the wiring described in [background technology]
The copper of the aspect that etched heavy is wanted and the etchant of 2 tunics of molybdenum.Particularly provide: containing hydrogen peroxide in etching solution
With the etching solution that also will not produce cupric oxalate (precipitate) on the basis of organic acid.
The etching solution of the present invention is conceived based on following technology: even if containing raw by the oxidation Decomposition of organic acid in etching solution
The material that one-tenth oxalic acid is also easily high with oxalic acid formation complex and dissolubility compared with copper, thus what suppression was caused by cupric oxalate
The generation of precipitate.The present inventor tests through numerous studies, found that: oxalic acid aluminum is easy network compared with cupric oxalate
Compound, and dissolubility is the highest, thus complete the present invention.
More specifically, the multilayer film etching solution comprising layers of copper and molybdenum layer of the present invention is characterised by, contains:
Hydrogen peroxide,
Acid organic acid,
Amines,
Hydrogen peroxide decomposing inhibitor,
Azole and
Comprise the anti-precipitation agent of aluminium salt.
It addition, the etching solution of the present invention can by preserve time or conveying time volume will not increase in the way of by the shape of concentrated solution
State is constituted.More specifically, the multilayer film comprising layers of copper and the molybdenum layer etching concentrated solution of the present invention is characterised by, described many
Tunic comprises molybdenum and copper,
Described etching concentrated solution contains:
Acid organic acid,
Amines,
Hydrogen peroxide decomposing inhibitor,
Azole,
Comprise aluminium salt anti-precipitation agent and
Water.
It addition, the multilayer film engraving method comprising layers of copper and molybdenum layer of the present invention is characterised by, including following operation:
Allotment etching concentrated solution, water and hydrogen peroxide, thus allocate the operation of multilayer film etching solution,
Described etching concentrated solution contains: acid organic acid,
Amines,
Hydrogen peroxide decomposing inhibitor,
Azole,
Comprise aluminium salt anti-precipitation agent and
Water；And,
Make the operation that aforenoted multi-layer film etching solution contacts with processed substrate.
The effect of invention
The multilayer film etching solution of the present invention contains: hydrogen peroxide, acid organic acid, amines, hydrogen peroxide decompose
Inhibitor, azole and comprise the anti-precipitation agent of aluminium salt, therefore, organic acid (acid organic acid) oxidized decomposition, even if result is raw
Become oxalic acid also to become oxalic acid aluminum, exist with the state being dissolved in etching solution.That is, the precipitate of cupric oxalate will not be produced.
Its result, does not has the generation of precipitate in etching solution, hole plug that will not produce pipe arrangement blocking, spray etc is no
Good situation.It is therefore not necessary to make Etaching device stop with such unfavorable condition as reason, it is possible to carry out stable production.
It addition, as acid organic acid, comprise at least one in glycolic, malonic acid, lactic acid, therefore, etched cloth
The cross sectional shape of line becomes positive cone, even if it addition, this shape of overetch is also maintained.
It addition, the multilayer film etching concentrated solution of the present invention is owing to getting rid of hydrogen peroxide and ormal weight from above-mentioned etching solution
Water, therefore, volume will not increase, it addition, also substantially without causing rheological parameters' change with time, it is possible to preserves or carries.
It addition, the multilayer film engraving method of the present invention allocates erosion owing to allocating above-mentioned etching concentrated solution and hydrogen peroxide
Carve liquid so that it is contact with processed substrate, therefore, it can be adjusted according to making by rear interpolation etching concentrated solution and hydrogen peroxide
With and the composition of etching solution that changes, bath life can be extended.
Accompanying drawing explanation
Fig. 1 is the schematic diagram in the cross section illustrating etched wiring.
Detailed description of the invention
Hereinafter the multilayer film etching solution of the present invention is illustrated.It should be noted that the following description illustrates this
One embodiment of bright etching solution, the scope in the purport without departing from the present invention can change following embodiment and enforcement
Example.The multilayer film etching solution of the present invention is characterised by, does not produce this point of precipitate in etching solution.
As be described hereinafter shown in embodiment, the reason of precipitate is precipitate azury i.e. cupric oxalate.For the present invention's
Multilayer film etching solution, even if organic acid generates oxalic acid oxidized decomposition, also forms the oxalic acid aluminum that dissolubility is high, thus, suppression
The generation of precipitate.
＜ hydrogen peroxide ＞
For the etching of copper, copper is oxidized, form copper oxide (CuO), and is dissolved by acid (organic acid).It addition, for molybdenum
Etching, oxidized and become molybdenum oxide (MoO3), be dissolved in water.Hydrogen peroxide makes as by the oxidant that copper and molybdenum aoxidize
With.Hydrogen peroxide is preferably 4.0 mass %～5.8 mass % of etching solution total amount.It should be noted that hydrogen peroxide is such as made
Water (hydrogen peroxide) of crossing for concentration 35% is supplied to.
＜ organic acid ＞
Organic acid has the effect that and is etched copper film, and adjusts the tapering in the cross section of etched wiring.Additionally
Think that also there is the function of the decomposition of a certain degree of suppression hydrogen peroxide.Organic acid uses acid organic acid.Need explanation
It is, in the multilayer film etching solution of the present invention, as anti-precipitation agent described later, it is also possible to comprise neutral organic acid.
As organic acid, in addition to the aliphatic carboxylic acid of carbon number 1～18, the aromatic carboxylic acid of carbon number 6～10, it is also possible to
Preferably enumerate: the aminoacid etc. of carbon number 1～10.
As the aliphatic carboxylic acid of carbon number 1～18, preferably can list: formic acid, acetic acid, propanoic acid, lactic acid, glycolic, two
Glycolic acid, acetone acid, malonic acid, butanoic acid, hydroxybutyric acid, tartaric acid, succinic 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, lauric acid,
Myristic acid, Palmic acid, stearic acid, oleic acid, linoleic acid, linolenic acid etc..
As the aromatic carboxylic acid of carbon number 6～10, preferably can list: benzoic acid, salicylic acid, mandelic acid, O-phthalic
Acid, M-phthalic acid, p-phthalic acid etc..
It addition, as the aminoacid of carbon number 1～10, carbamic acid, alanine, glycine, Radix Asparagi acyl preferably can be listed
Amine, aspartic acid, sarcosine, serine, glutamine, glutamic acid, 4-Aminobutanoicacid, imino-diacetic butanoic acid, arginine, bright ammonia
Acid, isoleucine, nitrilotriacetic acid etc..
In above-mentioned organic acid, as acid organic acid, can be suitable for utilizing glycolic, malonic acid, lactic acid.Especially by
It is applied in combination glycolic, malonic acid, lactic acid these three, it is possible to obtain the characteristic being suitable for simultaneously.It should be noted that preferably
It is to comprise relative to the acid organic acid that etching solution total amount is 1 mass % to 7 mass %.
During it should be noted that use glycolic, malonic acid, lactic acid, glycolic and malonic acid are relative to etching solution total amount
Being preferably 1 mass % to 5 mass %, lactic acid is preferably 0.1 mass % to 1.0 mass % relative to etching solution total amount.
＜ amines ＞
Amines undertakes the pH regulator of etching solution.As amines, can be suitable for utilizing the material of carbon number 2～10.
More specifically, preferably can list: 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-diaminobutane, 2,3-diaminobutane,
Five methylene diamine, 2,4-1,5-DAP, hexamethylene diamine, heptamethylene diamidogen, eight methylene diamine, nine methylene two
Amine, N-methyl ethylenediamine, N, N-dimethyl-ethylenediamine, trimethyl ethylenediamine, NEED, N, N-diethyl ethylenediamine,
Triethylethylenediamine, 1,2,3-triaminopropane, hydrazine, three (2-amino-ethyl) amine, four (amino methyl) methane, diethylidene three
Amine, trien, tetren, seven ethylidene eight amine, nine ethylidene ten amine, diazabicylo endecatylene etc. are many
Amine；Ethanolamine, N-methylethanolamine, N methyldiethanol amine, N-ehtylethanolamine, N-amino ethyl ethanolamine, N-propyl group second
Hydramine, N-butylethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol, N-methyl isopropyl hydramine, N-ethylisopropyl alcohol
Amine, N-propyl group isopropanolamine, 2-aminopropane-1-alcohol, N-methyl-2-amino-propane-1-alcohol, N-ethyl-2-amino-propan-
1-alcohol, 1-aminopropane-3-alcohol, N-methyl isophthalic acid-aminopropane-3-alcohol, N-ethyl-1-aminopropane-3-alcohol, 1-amino fourth
Alkane-2-alcohol, N-methyl isophthalic acid-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-butylamine-1-
Alcohol, N-ethyl-3-butylamine-1-alcohol, 1-butylamine-4-alcohol, N-methyl isophthalic acid-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) aminomethane, 1,2-diaminourea
Propane-3-alcohol, 1,3-diaminopropanes-2-alcohol, 2-(2-amino ethoxy) ethanol, 2-(2-aminoethylamino) ethanol, two
The alkanolamines such as glycol amine, these can be used alone or combine multiple use.In the middle of these, particularly preferred 1-amino-
2-propanol.It addition, preferably comprise the amines of 0.5 mass % to 2.0 mass % relative to etching solution total amount.
＜ hydrogen peroxide decomposing inhibitor ＞
In the multilayer film etching solution of the present invention, as oxidant, utilize hydrogen peroxide.Owing to hydrogen peroxide is carried out certainly
Status solution, therefore adds its decomposing inhibitor decomposed of suppression.It was also referred to as water stabilizer.This is in order to extend etching solution
Life-span.As main hydrogen peroxide decomposing inhibitor, except phenylurea, allylurea, 1, the urea system mistake such as 3-dimethyl urea, thiourea
Outside hydrogen oxide stabilizer, preferably can list: the lower alcohols etc. such as phenyl acetamide, phenylglycol, 1-propanol, 2-propanol.
Wherein particularly preferred phenylurea, it is further preferred that preferred compositions uses phenylurea and 1-propanol.Preferably with respect to erosion
Carve the hydrogen peroxide decomposing inhibitor that liquid total amount contains 0.5 mass % to 2.0 mass %.Thinking, these materials act on peroxide
Change hydrogen, suppress the generation of free radical thus suppress the decomposition of hydrogen peroxide.It should be noted that contain relative to etching solution total amount
During more than the phenylurea of 0.2 mass %, phenyl reacts with hydrogen peroxide, generates with the product of azole Yu hydrogen peroxide
Different precipitates.
＜ azole ＞
In the multilayer film etching solution of the present invention, in order to suppress the etch-rate of Cu, remove the residue of Mo and contain azole.
As azole, can be suitable for utilizing triazole type, four azoles, imidazoles, thiazoles etc..More specifically, following thing can be enumerated
Matter.As triazole type, can be suitable for utilizing 1H-benzotriazole, 5-methyl isophthalic acid H-benzotriazole, 3-amino-1H-triazole etc..
As four azoles, can be suitable for utilizing 1H-TETRAZOLE, 5-methyl isophthalic acid H-tetrazolium, 5-phenyl-1H-TETRAZOLE, 5-amino-
1H-TETRAZOLE etc..It addition, as imidazoles, can be suitable for utilizing 1H-imidazoles, 1H-benzimidazole etc..It addition, as four azoles,
Can be suitable for utilizing 1,3-thiazole, 4-methylthiazol etc..It should be noted that wherein, four azoles effect to suppression etch-rate
Fruit is high, particularly preferred 5-amino-1H-TETRAZOLE.
＜ anti-precipitation agent ＞
Time in etching solution based on hydrogen peroxide described above containing organic acid, etched wiring can be adjusted and cut
The tapering in face.But, organic acid is oxidized decomposition because of hydrogen peroxide, generates oxalic acid.By this oxalic acid and be etched and be present in
Copper ion in etching solution generates cupric oxalate, becomes precipitate.Aluminium ion is easy and oxalic acid formation complex compared with copper, and
Dissolubility is higher than cupric oxalate.
Therefore, in the etching solution of the present invention, even if containing aluminium salt in advance, producing copper ion by etching, also will not become
Precipitate (cupric oxalate).As aluminium salt, can be suitable for utilizing inorganic salt, aluctyl., the acetic acid such as aluminum sulfate, aluminum nitrate, aluminum chloride
The organic salt such as aluminum, aluminium carbonate etc..
＜ copper ion ＞
Multilayer film etching solution for the present invention, it is thus identified that: when etching carries out and contains Cu ion, Mo ion, according to
The increase of Cu ion concentration, etch-rate changes.For the operating of Etaching device, due to so that the change of etch-rate falls
The mode entering certain allowed band adds etching concentrated solution, hydrogen peroxide controls, and the most preferably also falls when new liquid
Enter this allowed band.Therefore, can be containing the Cu ion of prescribed limit in etching solution.Specifically, if 500ppm extremely
When 7000ppm, preferably 2000ppm to 4000ppm, the change of readily estimated etch-rate, therefore preferably.
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 etching
Normally used various additives in the range of performance.For water, due to for the purpose of Precision Machining, it is therefore desirable for for not exist
The material of foreign body.For preferred when pure water or ultra-pure water.
＜ pH, temperature ＞
The multilayer film of the present invention preferably uses by etching solution in the range of pH2～6, more preferably pH3～4.5.It addition, erosion
Carve liquid to 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 etching solution of the present invention uses hydrogen peroxide.Hydrogen peroxide carries out self and decomposes.Therefore, in etching solution
Comprise hydrogen peroxide decomposing inhibitor.But, during preservation, hydrogen peroxide and other liquid can be retained separately.Additionally, it is possible to
Preserve only retaining the raw material (referred to as " etching solution raw material ") eliminating water and copper ion.It should be noted that etching solution
Raw material can exist liquid charging stock and powder material.That is, the multilayer film etching solution of the present invention can merge etching solution raw material,
Water and hydrogen peroxide complete.
Alternatively, it is also possible to make etching solution raw material and water mixing in advance, make the solution of etching solution raw material.This solution can contain
The water of the ratio fewer than the ratio of the water of the etching solution shown in embodiment described later.The etching that will be made by etching solution raw material and water
The solution of liquid raw material is referred to as " etching concentrated solution ".Etching concentrated solution, compared with etching solution, does not has a hydrogen peroxide and volume is little, because of
This, preserve, convenient when carrying.Therefore, the multilayer film etching solution of the present invention can combine etching concentrated solution, water and hydrogen peroxide
And complete.
＜ engraving method ＞
The object of multilayer film etching solution using the present invention is: molybdenum becomes lower floor, copper becomes the multilamellar of copper/molybdenum on upper strata
Film.The thickness of the molybdenum of lower floor is thinner than the thickness of the copper on upper strata.The thickness of lower floor is set to t0, the thickness on upper strata is when being set to t1, t0/
T1 in the range of 0.01 to 0.2 the composition of scope.The scope of t0/t1 exceedes this scope, when Mo layer is blocked up, easily produces Mo layer
Residue, during on the contrary, cross the thinnest, it is impossible to play Cu layer as the effect of basal layer.
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, time actually used, they allotments are completed etching solution.For allotment
Method, as long as the concentration that the concentration of final hydrogen peroxide becomes regulation does not the most limit.
One example, the previously prepared etching concentrated solution being mixed with etching solution raw material in a certain amount of water are shown.Hydrogen peroxide
Generally with the concentration supply higher than the concentration of hydrogen peroxide of the multilayer film etching solution of the present invention.Therefore, ormal weight is allocated respectively
Hydrogen peroxide and etching concentrated solution.This operation can be referred to as the operation allocating multilayer film etching solution.
Copper ion can be when allocating etching concentrated solution with etching solution raw material and water or with etching concentrated solution and hydrogen peroxide
All can be mixed into during allotment etching solution.Can certainly add after allotment etching solution.It should be noted that using
When etching solution adds interpolation etching concentrated solution and hydrogen peroxide, it is also possible to be added without copper ion.This is because, copper ion is
It is present in etching solution.
When being etched, as described above, at pH2～6, etching solution is used under conditions of 20 DEG C to 40 DEG C.Therefore, it is desirable to
Etch is also heated at this temperature by object.The method making processed substrate contact with etching solution is not particularly limited.Permissible
As fountain, make from top etching solution that processed substrate is spread, or erosion can also be impregnated in for making processed substrate
The method carving the pond of liquid.The operation making multilayer film etching solution contact can also be referred to as with processed substrate.
It should be noted that processed substrate refers to, stacking molybdenum layer and layers of copper and at this stacked film on the base materials such as glass
The substrate of the state of the protective agent pattern that upper formation is formed for pattern.
Embodiment
The explanation ＞ of the various evaluation methodology of ＜
For the multilayer film etching solution of the present invention, the etch-rate of copper and molybdenum (is the most also recited as " CuE.R. "
" MoE.R. ") (nm/ minute), the cone angle (°) in cross section of etched wiring, the undercutting of molybdenum layer, the molybdenum layer of residual (claims on substrate
For " Mo residue "), overetch patience, the presence or absence of precipitate, hydrogen peroxide decomposition rate (quality %/sky) project in comment
Valency.
Etch-rate is measured as described below.First, by sputtering method, at the silicon being formed with heat oxide film 100nm
On wafer with copper as 300nm, the molybdenum thickness as 150nm form monofilm respectively.Make this copper film and molybdenum film and 30 DEG C (according to comparing
Example also has the situation of 35 DEG C) etching solution contact 20 to 60 seconds.
Constant current is used to apply 4 terminal 4 sonde method resistrivity meter (Mitsubishi Chemical of mode
Analytech Co., Ltd. manufacture: MCP-T610 type) measure the resistance value of film before and after etching.Change according to this resistance value is calculated
Go out Thickness Variation, calculate etch-rate.
Cone angle is measured as described below.First, molybdenum is become with the thickness of 20nm by sputtering method on the glass substrate
Film, continues the thickness with 300nm thereon by copper film forming, the multilayer film sample of making Cu/Mo.This copper film is formed pattern shape
Become the protective agent of wiring shape, form the base material of cone angle evaluation.That is, base material is by substrate, molybdenum film, copper film thereon and copper film
On through pattern formed protection oxidant layer constitute.Make this base material impregnated in etching solution with the time appropriately etched, carry out
Etching.Clean the sample after etching and make it be dried, being then cut off wiring portion, observe and cut cross section.
Cut the observation in cross section use SEM (Hitachi, Ltd. manufacture: SU8020 type) accelerating potential 1kV, 30000～
Carry out under conditions of 50000 times.It should be noted that appropriate etching is the time that self etching starts to film transmission light.With
It is visually confirmed to be the moment of film transmission light.
Cross sectional shape will be cut and be shown in Fig. 1.As shown in (a) of Fig. 1, formed by substrate 1 and etched inclined plane 6
Angle 5 is as cone angle (°).If cone angle 5 is 30～60 °, then it is judged as circle (zero).Outside if the scope of this angle, then sentence
Break for fork (×).It should be noted that " justifying " refers to successfully or qualified, " pitching " refers to failure or defective.Following evaluation is also
Identical.It should be noted that in (a) of Fig. 1, Mo layer symbol 3 represents, Cu layer symbol 2 represents, protective agent symbol 4 table
Show.
The undercutting of molybdenum layer refers to, by fast-etching between molybdenum layer 3 and substrate 1 as shown in the symbol 10 of (b) of Fig. 1
State (inverted cone).Evaluation can be carried out when the evaluation of cone angle 5 simultaneously.For the undercutting of molybdenum layer, if at the 30000 of SEM
Times to undiscovered in the observation of 50000 times, be judged as circle (zero), if be found, be judged as fork (×).
For Mo residue, in utilizing the observation of optical microscope and SEM, if it is confirmed that be then judged to fork to residue
(×), then it is judged to circle (zero) without confirming residue.It should be noted that optical microscope about 100 times times
Observe under rate, with bright field and dark ground is observed.It addition, in SEM, observe with 30000 times to 50000 times.
Overetch patience (also referred to as " O.E. patience ") refers to, the time of 2 times of observation time needed for appropriate etching
Cone angle when being etched, the undercutting of molybdenum layer, Mo residue, if being all evaluated as " justifying ", be judged as circle (zero).If any 1
Individual be evaluated as " pitching " then be judged as fork (×).
For the presence or absence of precipitate, after allotment etching solution, in bottle, room temperature places the stipulated time (3 hours) in advance, with mesh
Depending on whether producing precipitate azury in judging bottle.In the case of producing precipitate, use filter paper filtering etching solution, make on filter paper
The foreign body of residual carries out pure water cleaning, drying at room temperature, utilizes the FT-IR (IR that Shimadzu Scisakusho Ltd manufactures
Affinity), SEM-EDX (HORIBA, Ltd manufacture) analyzes gained crystal thing, powder body.Precipitate is without by visual observation
To be then judged as circle (zero), situation about being visually confirmed to be judged as fork (×).
For etching solution, it is important that the cross sectional shape of the aspect and wiring that do not produce precipitate is suitable for, for extension slot
In the liquid life-span, the decomposition rate of hydrogen peroxide also becomes important project.Being herein incorporated by reference, hydrogen peroxide decomposition rate also serves as
Assessment item is investigated.
Hydrogen peroxide decomposition rate is carried out as follows mensuration: using potassium permanganate as titer reagent, uses automatic titration device
(GT-200 that Mitsubishi Chemical Analytech Co., Ltd. manufactures), measure after just allocating etching solution and
At 35 DEG C after the stipulated time concentration of hydrogen peroxide of (about 24 hours).Then, according to the variable quantity of concentration of hydrogen peroxide
Calculate decomposition rate (quality %/sky).The decomposition rate of concentration of hydrogen peroxide is if then thinking below 1 mass %/sky in amount
In product scale no problem.
(embodiment 1)
To comprise as acid organic acid
Glycolic 1.87 mass %,
Malonic acid 3.41 mass %,
Lactic acid 0.69 mass %,
As amines
1-amino-2-propanol 2.20 mass %,
As crossing water stabilizer
Phenylurea 0.10 mass %,
As azole
1H-TETRAZOLE-5-amine monohydrate (CH3N5·H2O: following identical) 0.12 mass %
As anti-precipitation agent
Aluminum nitrate 0.28 mass %
Etching solution raw material and water 86.03 mass % allocate, preparation etching concentrated solution.It should be noted that herein, water is also
Water including the hydrogen peroxide of the following stated.Below example is the most identical with in comparative example.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And, add copper sulfate, with copper ion concentration (for " Cu concentration " described in table.The most identical.) mode that reaches 2000ppm carries out
Preparation.It addition, addition molybdenum trisulfate, with molybdenum concentration (for " Mo concentration " described in table.The most identical.) mode that reaches 200ppm enters
Row preparation.It addition, liquid temperature uses at 35 DEG C.The result that each composition accounts for the overall concentration of etching solution and each evaluation item is shown in
Table 1.
(embodiment 2)
To comprise as acid organic acid
Glycolic 1.87 mass %,
Malonic acid 3.41 mass %,
Lactic acid 0.69 mass %,
As amines
1-amino-2-propanol 2.20 mass %,
As crossing water stabilizer
Phenylurea 0.10 mass %,
As azole
1H-TETRAZOLE-5-amine monohydrate 0.12 mass %
As anti-precipitation agent
Aluctyl. 0.22 mass %
Etching solution raw material and water 86.09 mass % allocate, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And, add copper sulfate, be prepared in the way of copper ion concentration reaches 2000ppm.It addition, addition molybdenum trisulfate, with molybdenum concentration
The mode reaching 200ppm is prepared.It addition, liquid temperature uses at 35 DEG C.Each composition is accounted for the overall concentration of etching solution with each
The result evaluating item is shown in table 1.
(embodiment 3)
As comprising as acid organic acid
Glycolic 1.87 mass %,
Malonic acid 3.41 mass %,
Lactic acid 0.69 mass %,
As amines
1-amino-2-propanol 2.20 mass %,
As crossing water stabilizer
Phenylurea 0.10 mass %,
As azole
1H-TETRAZOLE-5-amine monohydrate 0.12 mass %
As anti-precipitation agent
Beta-alanine 0.56 mass %,
Aluminum nitrate 0.28 mass %
Etching solution raw material and water 85.47 mass % allocate, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And, add copper sulfate, be prepared in the way of copper ion concentration reaches 2000ppm.It addition, addition molybdenum trisulfate, with molybdenum concentration
The mode reaching 200ppm is prepared.It addition, liquid temperature uses at 35 DEG C.Each composition is accounted for the overall concentration of etching solution with each
The result evaluating item is shown in table 1.
(embodiment 4)
To comprise as acid organic acid
Glycolic 1.87 mass %,
Malonic acid 3.41 mass %,
Lactic acid 0.69 mass %,
As amines
1-amino-2-propanol 2.20 mass %,
As crossing water stabilizer
Phenylurea 0.10 mass %,
As azole
1H-TETRAZOLE-5-amine monohydrate 0.12 mass %
As anti-precipitation agent
Beta-alanine 0.56 mass %,
Aluctyl. 0.22 mass %
Etching solution raw material and water 85.53 mass % allocate, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And, add copper sulfate, be prepared in the way of copper ion concentration reaches 2000ppm.It addition, addition molybdenum trisulfate, with molybdenum concentration
The mode reaching 200ppm is prepared.It addition, liquid temperature uses at 35 DEG C.Each composition is accounted for the overall concentration of etching solution with each
The result evaluating item is shown in table 1.
(embodiment 5)
To comprise as acid organic acid
Glycolic 1.87 mass %,
Malonic acid 3.41 mass %,
Lactic acid 0.08 mass %,
As amines
1-amino-2-propanol 2.20 mass %,
As crossing water stabilizer
Phenylurea 0.10 mass %,
As azole
1H-TETRAZOLE-5-amine monohydrate 0.12 mass %
As anti-precipitation agent
Beta-alanine 0.56 mass %,
Aluctyl. 0.87 mass %
Etching solution raw material and water 85.49 mass % allocate, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And, add copper sulfate, be prepared in the way of copper ion concentration reaches 2000ppm.It addition, addition molybdenum trisulfate, with molybdenum concentration
The mode reaching 200ppm is prepared.It addition, liquid temperature uses at 35 DEG C.Each composition is accounted for the overall concentration of etching solution with each
The result evaluating item is shown in table 1.
(comparative example 1)
To comprise as mineral acid
Nitric acid 0.06 mass %,
As acid organic acid
Glycolic 1.87 mass %,
Malonic acid 3.42 mass %
Lactic acid 0.81 mass %
As amines
1-amino-2-propanol 2.28 mass %,
As crossing water stabilizer
Phenylurea 0.10 mass %,
As azole
1H-TETRAZOLE-5-amine monohydrate 0.12 mass %
Etching solution raw material and water 86.04 mass % allocate, preparation etching concentrated solution.This comparative example 1 does not comprise quite
Material in anti-precipitation agent.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And, add copper sulfate, be prepared in the way of copper ion concentration reaches 2000ppm.It addition, addition molybdenum trisulfate, with molybdenum concentration
The mode reaching 200ppm is prepared.It addition, liquid temperature uses at 35 DEG C.Each composition is accounted for the overall concentration of etching solution with each
The result evaluating item is shown in table 2.
(comparative example 2)
To comprise as acid organic acid
Glycolic 1.87 mass %,
Malonic acid 3.41 mass %
Lactic acid 0.87 mass %
As amines
1-amino-2-propanol 2.20 mass %,
As crossing water stabilizer
Phenylurea 0.10 mass %,
As azole
1H-TETRAZOLE-5-amine monohydrate 0.12 mass %
As anti-precipitation agent
The etching solution raw material of Beta-alanine 0.55 mass % is allocated with water 85.58 mass %, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And, add copper sulfate, be prepared in the way of copper ion concentration reaches 2000ppm.It addition, addition molybdenum trisulfate, with molybdenum concentration
The mode reaching 200ppm is prepared.It addition, liquid temperature uses at 35 DEG C.Each composition is accounted for the overall concentration of etching solution with each
The result evaluating item is shown in table 2.
(comparative example 3)
To comprise as acid organic acid
Glycolic 1.87 mass %,
Malonic acid 3.41 mass %
Lactic acid 0.87 mass %
As amines
1-amino-2-propanol 2.20 mass %,
As crossing water stabilizer
Phenylurea 0.10 mass %,
As azole
1H-TETRAZOLE-5-amine monohydrate 0.12 mass %
As anti-precipitation agent
The etching solution raw material of glycine 0.55 mass % is allocated with water 85.58 mass %, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And, add copper sulfate, be prepared in the way of copper ion concentration reaches 2000ppm.It addition, addition molybdenum trisulfate, with molybdenum concentration
The mode reaching 200ppm is prepared.It addition, liquid temperature uses at 35 DEG C.Each composition is accounted for the overall concentration of etching solution with each
The result evaluating item is shown in table 2.
(comparative example 4)
To comprise as acid organic acid
Glycolic 1.87 mass %,
Malonic acid 3.41 mass %
Lactic acid 0.87 mass %
As amines
1-amino-2-propanol 2.20 mass %,
As crossing water stabilizer
Phenylurea 0.10 mass %,
As azole
1H-TETRAZOLE-5-amine monohydrate 0.12 mass %
As anti-precipitation agent
The etching solution raw material of EDTA (ethylenediaminetetraacetic acid) 0.55 mass % is allocated with water 85.58 mass %, preparation etching
Concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And, add copper sulfate, be prepared in the way of copper ion concentration reaches 2000ppm.It addition, addition molybdenum trisulfate, with molybdenum concentration
The mode reaching 200ppm is prepared.It addition, liquid temperature uses at 35 DEG C.Each composition is accounted for the overall concentration of etching solution with each
The result evaluating item is shown in table 2.
(comparative example 5)
Want to make and comprise as acid organic acid
Glycolic 1.87 mass %,
Malonic acid 3.41 mass %
Lactic acid 0.69 mass %
As amines
1-amino-2-propanol 2.20 mass %,
As crossing water stabilizer
Phenylurea 0.10 mass %,
As azole
1H-TETRAZOLE-5-amine monohydrate 0.12 mass %
As anti-precipitation agent
The etching solution raw material of aluminium hydroxide, but aluminium hydroxide does not dissolves, it is impossible to make etching solution raw material.Show the result in table
3。
(comparative example 6)
To comprise as acid organic acid
Glycolic 1.87 mass %,
Malonic acid 3.41 mass %
Lactic acid 0.69 mass %
As amines
1-amino-2-propanol 2.20 mass %,
As crossing water stabilizer
Phenylurea 0.10 mass %,
As azole
1H-TETRAZOLE-5-amine monohydrate 0.12 mass %
As anti-precipitation agent
The etching solution raw material of nickel sulfate 0.38 mass % is allocated with water 91.23 mass %, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.3 mass %.Enter
And, add copper sulfate, be prepared in the way of copper ion concentration reaches 2000ppm.It addition, addition molybdenum trisulfate, with molybdenum concentration
The mode reaching 200ppm is prepared.It addition, liquid temperature uses at 35 DEG C.Each composition is accounted for the overall concentration of etching solution with each
The result evaluating item is shown in table 3.
(comparative example 7)
To comprise as oxidant
Copper sulfate (CuSO4) 1.35 mass %,
As acid organic acid
Citric acid 10.00 mass %,
Glycine 15.00 mass %
Etching solution raw material and water 75.00 mass % allocate, prepare etching solution.
And then, add copper sulfate, be prepared in the way of copper ion concentration reaches 5000ppm.It addition, liquid temperature is at 30 DEG C
Lower use.The result that each composition accounts for the overall concentration of etching solution and each evaluation item is shown in table 4.
(comparative example 8)
To comprise as oxidant
Copper sulfate (CuSO4) 5.88 mass %,
As acid organic acid
Citric acid 10.00 mass %,
Glycine 15.00 mass %
Etching solution raw material and water 75.00 mass % allocate, prepare etching solution.
And then, add copper sulfate, be prepared in the way of copper ion concentration reaches 24000ppm.It addition, liquid temperature is 30
Use at DEG C.The result that each composition accounts for the overall concentration of etching solution and each evaluation item is shown in table 4.
(comparative example 9)
To comprise as oxidant
Copper chloride (CuCl2) 1.10 mass %,
As acid organic acid
Citric acid 10.00 mass %,
Glycine 15.00 mass %
Etching solution raw material and water 73.90 mass % allocate, prepare etching solution.
And then, add Cu-lyt., be prepared in the way of copper ion concentration reaches 5000ppm.It addition, liquid temperature is 30
Use at DEG C.The result that each composition accounts for the overall concentration of etching solution and each evaluation item is shown in table 4.
(comparative example 10)
To comprise as oxidant
Copper chloride (CuCl2) 5.10 mass %,
As acid organic acid
Citric acid 10.00 mass %,
Glycine 15.00 mass %
Etching solution raw material and water 69.90 mass % allocate, prepare etching solution.
And then, add Cu-lyt., be prepared in the way of copper ion concentration reaches 24000ppm.It addition, liquid temperature exists
Use at 30 DEG C.The result that each composition accounts for the overall concentration of etching solution and each evaluation item is shown in table 4.
(comparative example 11)
To comprise as oxidant
Copper chloride (CuCl2) 1.20 mass %,
As acid organic acid
Citric acid 10.00 mass %,
Beta-alanine 15.00 mass %
Etching solution raw material and water 73.80 mass % allocate, prepare etching solution.
And then, add Cu-lyt., be prepared in the way of copper ion concentration reaches 5000ppm.It addition, liquid temperature is 30
Use at DEG C.The result that each composition accounts for the overall concentration of etching solution and each evaluation item is shown in table 4.
(comparative example 12)
To comprise as oxidant
Copper chloride (CuCl2) 5.00 mass %,
As acid organic acid
Citric acid 10.00 mass %,
Beta-alanine 15.00 mass %
Etching solution raw material and water 70.00 mass % allocate, prepare etching solution.
And then, add Cu-lyt., be prepared in the way of copper ion concentration reaches 24000ppm.It addition, liquid temperature exists
Use at 30 DEG C.The result that each composition accounts for the overall concentration of etching solution and each evaluation item is shown in table 4.
[table 1]
[table 2]
[table 3]
[table 4]
＜ result ＞
Embodiment 1 to embodiment 5 is the multilayer film etching solution of the present invention.The most do not produce light blue owing to comprising aluminium salt
The precipitate (cupric oxalate) of color.During it addition, be simultaneously used as Beta-alanine (embodiment 3 to 5) of neutral organic acid with aluminium salt,
Produce unfavorable condition the most especially.It addition, acid organic acid uses glycolic, malonic acid, lactic acid these 3 kinds simultaneously.They institute
Have in sample and all there is no precipitate, and the project of cone angle, Mo undercutting, Mo residue, O.E. patience is also circle evaluation.And then,
Hydrogen peroxide decomposition rate, again smaller than 0.1 mass %/sky, can obtain desired result.
It addition, overetch patience is good, therefore, from the time spent by appropriate etching to 2 times of times permissible
It is etched with maintaining good cone angle.It addition, for the etching solution of these embodiments, even if the Film Thickness Ratio (t0/ of Mo Yu Cu
T1) different from the situation of embodiment (20/300), if Film Thickness Ratio is between 0.01 to 0.2, the cone of 30 ° to 60 ° can be realized
Degree.
Comparative example 1 to comparative example 4 is by interpolation organic acid, chelating agent thus to have attempted the example of the seizure of copper ion.
Expect the reaction of its suppression copper ion and oxalic acid.Comparative example 1 is the situation of not aluminium containing salt.As composition, it is contained in patent documentation
4.In comparative example 1, it is impossible to suppression oxalic acid and the reaction of copper, therefore generate cupric oxalate and produce precipitate.
It addition, the example that comparative example 2 is the effect investigating the Beta-alanine that the anti-precipitation agent as embodiment 3 to 5 uses.
When being used together with aluminium salt, the generation of suppression cupric oxalate, but when Beta-alanine is independent, it is impossible to the generation of suppression cupric oxalate.Thus
Understand, in embodiment each sample, suppressed the generation of cupric oxalate by aluminium salt.
Comparative example 2 to 4 is to add glycine, the example of EDTA as anti-precipitation agent.Particularly, EDTA is as chelating agent
It is known, by preferential for copper complexation, can expect to suppress the effect of the generation of cupric oxalate.But, Beta-alanine, glycine,
EDTA all cannot suppress to separate out.It addition, their interpolation can produce Mo residue.That is, there is the probability of the etching of suppression Mo.
Comparative example 5 and 6 is 1 research of aluminium salt kind.In comparative example 5, use aluminium hydroxide as aluminium salt.But, hydrogen
Aluminium oxide even cannot be dissolved in this etching solution and cannot make etching solution.Comparative example 6 is to taste as the metallic element beyond aluminum
Try the result of nickel.As anti-precipitation agent, use nickel sulfate.But, for nickel sulfate, it is impossible to the generation of suppression cupric oxalate.
Comparative example 7 to 12 is the result of the example having attempted the copper etchant solution not using hydrogen peroxide.Etching solution by oxidant,
Acid organic acid and water are constituted.In comparative example 7 and 8, as oxidant, use copper sulfate.It addition, in comparative example 9 to 12, use
Cu-lyt..In comparative example 7 to 12, with the copper concentration in etching solution be up to 5000 or the state of 24000ppm is etched.
By adjusting oxidant and the concentration of organic acid, thus it is possible to vary the etch-rate of copper.But, molybdenum cannot lose completely
Carve.On the other hand, due to without hydrogen peroxide, malonic acid, glycols, therefore, entirely without the precipitate of cupric oxalate.More than as,
Copper can be etched by etching solution based on oxidant and the copper of organic acid, but becomes molybdenum and the situation of this 2 Rotating fields of copper
Under, as etching solution, it is impossible to use.
Industrial applicability
The based article of the etching solution of the present invention no matter FPD such as liquid crystal display, plasma scope, organic EL, makes
Can also extensively utilize with under the situation of the wiring 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 (11)
1. the multilayer film etching solution comprising molybdenum and copper, it is characterised in that contain:
Hydrogen peroxide,
Acid organic acid,
Amines,
Hydrogen peroxide decomposing inhibitor,
Azole and
Comprise the anti-precipitation agent of aluminium salt.
The multilayer film etching solution comprising molybdenum and copper the most according to claim 1, it is characterised in that described aluminium salt comprises breast
Any one in acid aluminum or aluminum nitrate.
The multilayer film etching solution comprising molybdenum and copper the most according to claim 1 and 2, it is characterised in that described acidity has
Machine acid comprises at least one in glycolic, malonic acid, lactic acid.
The multilayer film etching solution comprising molybdenum and copper the most according to any one of claim 1 to 3, it is characterised in that institute
Stating amines is 1-amino-2-propanol.
The multilayer film etching solution comprising molybdenum and copper the most according to any one of claim 1 to 4, it is characterised in that institute
Stating hydrogen peroxide decomposing inhibitor is phenylurea.
The multilayer film etching solution comprising molybdenum and copper the most according to any one of claim 1 to 5, it is characterised in that institute
Stating azole is 1H-TETRAZOLE-5-amine.
The multilayer film etching solution comprising molybdenum and copper the most according to any one of claim 1 to 6, it is characterised in that institute
State in anti-precipitation agent and comprise Beta-alanine.
The multilayer film etching solution comprising molybdenum and copper the most according to any one of claim 1 to 7, it is characterised in that also
Comprise the copper ion of 500～7000ppm.
9. a multilayer film etching concentrated solution, it is characterised in that described multilayer film comprises molybdenum and copper,
Described etching concentrated solution contains:
Acid organic acid,
Amines,
Hydrogen peroxide decomposing inhibitor,
Azole,
Comprise aluminium salt anti-precipitation agent and
Water.
10. the multilayer film engraving method comprising molybdenum and copper, it is characterised in that include following operation:
Allotment etching concentrated solution, water and hydrogen peroxide, thus allocate the operation of multilayer film etching solution,
Described etching concentrated solution contains: acid organic acid,
Amines,
Hydrogen peroxide decomposing inhibitor,
Azole,
Comprise aluminium salt anti-precipitation agent and
Water；And,
Make the operation that described multilayer film etching solution contacts with processed substrate.
The 11. multilayer film engraving methods comprising molybdenum and copper according to claim 10, it is characterised in that make described multilamellar
The operation that film etching solution contacts with processed substrate in the scope that pH is 2 to 6 and the liquid temperature of described multilayer film etching solution is
Carry out under conditions of 20 DEG C to 40 DEG C.
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| 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 true CN106255777A (en) | 2016-12-21 |
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| US10655231B2 (en) | 2014-11-18 | 2020-05-19 | Kanto Kagaku Kabushiki Kaisha | Etchant composition for multilayered metal film of copper and molybdenum, method of etching using said composition, and method for prolonging life of said composition |
| CN107075693A (en) * | 2014-11-18 | 2017-08-18 | 关东化学株式会社 | Copper, molybdenum stacked film etchant, the engraving method using said composition and extend said composition life-span method |
| CN107075693B (en) * | 2014-11-18 | 2019-07-12 | 关东化学株式会社 | Copper, molybdenum stacked film etchant, using the composition engraving method and extend the composition service life method |
| 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 |
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| CN109423648A (en) * | 2017-09-04 | 2019-03-05 | 三星显示有限公司 | Etchant composition and method of manufacturing metal pattern and thin film transistor substrate using the same |
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| 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 |
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| CN110923713A (en) * | 2019-12-31 | 2020-03-27 | 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 |
| CN116240547A (en) * | 2022-12-25 | 2023-06-09 | 湖北兴福电子材料股份有限公司 | Copper etching solution and preparation method 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI560318B (en) | 2016-12-01 |
| CN106255777B (en) | 2018-03-20 |
| JP2015209568A (en) | 2015-11-24 |
| WO2015162934A1 (en) | 2015-10-29 |
| TW201606135A (en) | 2016-02-16 |
| JP5866566B2 (en) | 2016-02-17 |
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