CN105765107A - Multilayer-film etchant, concentrated etchant, and etching method - Google Patents
Multilayer-film etchant, concentrated etchant, and etching method Download PDFInfo
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- CN105765107A CN105765107A CN201380081154.1A CN201380081154A CN105765107A CN 105765107 A CN105765107 A CN 105765107A CN 201380081154 A CN201380081154 A CN 201380081154A CN 105765107 A CN105765107 A CN 105765107A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
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Abstract
When an etchant that alone can etch a multilayer film comprising a copper layer and a molybdenum layer is used during mass production, it is important for the cross-sectional shape of an edge after etching to satisfy the shape requirement of having a forward taper without an undercut, and that no precipitate be formed in the etchant. A multilayer-film etchant containing a copper layer and a molybdenum layer contains hydrogen peroxide, an inorganic acid, an acidic organic acid, a neutral organic acid, an amine compound, and a hydrogen peroxide decomposition inhibitor, but not an azole compound, and therefore no reaction products are generated from a reaction with the hydrogen peroxide, and no precipitates form in the etchant. Furthermore, the cross-sectional shape of the edge after etching can be formed into a desirable forward tapering shape. Containing no phosphorus compounds or fluorine compounds, the etchant will case minimal damage to the environment when disposed.
Description
Technical field
The present invention relates to use when the multilayer film of layers of copper and the molybdenum layer used in the wiring purposes of the flat faced display to liquid crystal, organic EL etc. is etched, multilayer film etching solution and etching concentrated solution and engraving method.
Background technology
For the TFT (thin film transistor (TFT), Thinfilmtransistor) of the flat faced display (FPD) of liquid crystal, organic EL (electroluminescent, Electro-Luminescence) etc., employ aluminum as wiring material.In recent years, the FPD of big picture and high-fineness popularizes, it is desirable to the wiring material used is the material that resistance ratio aluminum is low.Therefore, in recent years, the low copper of resistance ratio aluminum is employed as wiring material.
When using copper as wiring material, can produce and the bonding force between substrate and these 2 problems of the diffusion to semiconductor substrate.That is, when using in grid wiring, even if using the sputtering method that the collision energy of base material is bigger, there is also the situation that bonding force is insufficient between the substrates such as glass.It addition, when using during source/drain connects up, the problem that the copper that can produce to adhere to spreads, can change the electric design load of quasiconductor to the silicon as substrate.
In order to solve this problem, have employed initial formation molybdenum layer on substrate, semiconductor substrate in advance at present, be then formed on the multiple structure of layers of copper.
The multilayer film adopting sputtering method to be formed is carried out wet etching and is formed by being routed through of FPD.This is because: owing to can disposable large area be formed, therefore, it is possible to shorten operation.Herein, in the wet etching of wiring, it is important that following aspect.
(1) machining accuracy is highly consistent.
(2) the wiring cross section after processing is the positive cone of predetermined angular.
(3) owing to containing copper ion in etching solution, therefore etching performance is not easily deteriorated (bath life length).
(4) generation of precipitate is few.
Highly consistent as the machining accuracy of the 1st project it is not only carrying out wet etching but also adding, what carry out tiny area, the project necessarily required man-hour.As wiring being shaped as of cross section of the 2nd project, when forming the wiring of large-area FPD in the lump, the shape needed to carry out certain wiring to be formed.This is because, the part at the etched edge of the multilayer film of layers of copper and molybdenum layer can from substrate formed with the positive cone of 30～60 degree time, even if occurring, etching is bad or copper is different with the balance of the etch-rate of molybdenum, it is also possible to guarantee the surplus that can ensure that product quality.
3rd project is the problem of etching solution its shelf-life.In order to large-area substrate is etched, it is necessary to substantial amounts of etching solution.These etching solutions can also recycle from the viewpoint of cost.It is able to maintain that the cost step-down of period (life-span) elder as far as possible of its etching performance is honest and clean.
It addition, the 4th project is not only the problem for maintaining Etaching device, the also problem for being related to the quality problems of product.When producing precipitate because of etching, it may occur that the pipe arrangement of Etaching device blocking or make the hole plug of spray nozzle of sprinkling etching solution.It is relevant with the rising of cost that these phenomenons become the reason that Etaching device shuts down.It addition, when precipitate is attached on product by etching solution, become the reason of short circuit, broken string, the problem becoming the quality being directly connected to product.
Etching solution about layers of copper and the multilayer film of molybdenum layer, it was recently reported that containing the etching solution (patent documentation 1: Japanese Unexamined Patent Publication 2002-302780 publication (Japanese Patent 4282927)) of at least one in neutral salt and organic acid and hydrogen peroxide.
It addition, report the etching solution of following copper molybdenum film: it contains using ormal weight respectively: hydrogen peroxide, organic acid, phosphate, the water solublity cyclic amine compound as the 1st additive, a kind of water soluble compound contained in amino and carboxyl as the 2nd additive, fluorine compounds and deionized water (patent documentation 2: Japanese Unexamined Patent Publication 2004-193620 publication (Japanese Patent 4448322)).
It addition, report the multiple film wiring etching solution of the molybdenum/copper/molybdenum nitride containing hydrogen peroxide, organic acid, three azole compounds, fluorine compounds and ultra-pure water (patent documentation 3: Japanese Unexamined Patent Publication 2007-005790 publication (Japanese Patent 5111790)).
Additionally, there is also reports that 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 organic acid in succinic acid, glycolic, lactic acid, malonic acid and malic acid；(D) amines that carbon number 2～10 and amino and hydroxyl have with they total group numbers for the mode of more than two；(E) 5-amino-1H-TETRAZOLE；And (F) stabilizer of hydrogen peroxide, pH is 2.5～5 (patent documentations 4: Japanese Patent 5051323).
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2002-302780 publication (Japanese Patent 4282927)
Patent documentation 2: Japanese Unexamined Patent Publication 2004-193620 publication (Japanese Patent 4448322)
Patent documentation 3: Japanese Unexamined Patent Publication 2007-005790 publication (Japanese Patent 5111790)
Patent documentation 4: Japanese Patent 5051323
Summary of the invention
The problem that invention to solve
Patent documentation 1 only discloses when hydrogen peroxide and organic acid mixed liquor, if regulating the ratio of hydrogen peroxide, then the content that can simultaneously copper and molybdenum be etched, entirely without the open composition about concrete etching solution.
Patent documentation 2,3 uses fluorine compounds in the composition.Therefore, do not only have glass substrate, silicon substrate also can etched problem, also produce the environmental pressure when etching solution discarded and become big problem.
Patent documentation 4 have studied the etching of the multilayer film of layers of copper and molybdenum layer in detail.But, the composition of the etching solution of patent documentation 4 produces a large amount of problems producing precipitate in etching solution.
It addition, when using phosphorus compound, fluorine compounds as the composition of etching solution, it is easy to obtain the performance as etching solution, however when discarded, the burden of environment is big.
For solving the scheme of problem
The present invention expects in view of above-mentioned problem, which provide meet the point that the wet etching of wiring of narration in [background technology] is important, comprise layers of copper and the etchant of the multilayer film of molybdenum layer.Specifically provide in etching solution, do not produce precipitate, and to the also little etching solution of the burden of environment and its concentrated solution and engraving method when discarded.
More specifically, the multilayer film etching solution of the present invention, described multilayer film comprises layers of copper and molybdenum layer, it is characterised in that
It contains hydrogen peroxide, mineral acid, acid organic acid, neutral organic acid, amines and peroxide decomposition inhibitor.
It addition, the etching solution of the present invention can when stored or conveying time volume do not increase ground, constituted with the state of concentrated solution.More specifically, the multilayer film of present invention etching concentrated solution, described multilayer film comprises layers of copper and molybdenum layer, it is characterised in that
It contains mineral acid, acid organic acid, neutral organic acid, amines, peroxide decomposition inhibitor and water.
It addition, the multilayer film engraving method of the present invention, described multilayer film comprises layers of copper and molybdenum layer, it is characterised in that it includes following operation:
Etching concentrated solution containing mineral acid, acid organic acid, neutral organic acid, amines, peroxide decomposition inhibitor and water is concocted with water and hydrogen peroxide and concocted multilayer film etching solution；And
Aforenoted multi-layer film etching solution is made to contact with processed substrate.
The effect of invention
For the etching solution of the present invention, the cross sectional shape of the wiring after etching is positive cone, even if it addition, carry out overetch, its shape is also maintained.It addition, when using together with hydrogen peroxide, due to the composition for not containing the azole compounds generating precipitate, therefore do not produce precipitate in etching solution, do not produce this unfavorable condition of hole plug of pipe arrangement blocking, spray nozzle.Therefore, it is not necessary to make the operating of Etaching device stop with being produced as reason of precipitate, it is possible to carry out stable production.
It addition, the etching concentrated solution of the present invention is compared to above-mentioned etching solution, owing to not containing the water of hydrogen peroxide and ormal weight, therefore, it is possible to volume does not increase and does not carry out preserving or carrying while rheological parameters' change with time does not also occur substantially.Further, since concentrated solution and hydrogen peroxide separately process will be etched, therefore, it is possible to be easily adjusted the concentration of the etching solution of composition concentration change because of use.
Additionally, engraving method for the present invention, owing to above-mentioned etching concentrated solution and hydrogen peroxide are concocted and are concocted etching solution, it is made to contact with processed substrate, therefore the etching solution of stable composition can be prepared at any time, the cross section of the wiring formed has positive cone, even if carrying out overetch, it is also possible to carry out the etching that cone angle maintains the scope of suitable angle.
It addition, the etching solution of the present invention is not owing to containing the materials such as phosphorus compound, chlorine compound, fluorine compounds, therefore there is advantage when discarded, the burden of environment is light.
Accompanying drawing explanation
Fig. 1 is the schematic diagram representing the cross section by etching the wiring formed.
Detailed description of the invention
Hereinafter the etching solution of the present invention is illustrated.It should be noted that the following description illustrates an embodiment of the etching solution of the present invention, the scope in the purport without departing from the present invention can change following embodiment and embodiment.The 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 strong reactant that reason is azole compounds and hydrogen peroxide enlightening precipitate.Therefore, the etching solution of the present invention does not contain azole compounds.
It addition, in order to alleviate environmental pressure, do not contain phosphorus compound, fluorine compounds, chlorine compound yet.But, the environmental pressure when etching performance, product quality are not affected or be discarded is below the benchmark that various countries specify, it is possible to contain.It addition, when being such amount, it is possible to it is construed to not contain.
<hydrogen peroxide>
For the etching of copper, copper is oxidized, form copper oxide (CuO), by inorganic acid solution.It addition, for the etching of molybdenum, oxidized and become molybdenum oxide (MoO3), be dissolved in water.Hydrogen peroxide uses as by the oxidant that copper and molybdenum aoxidize.Hydrogen peroxide is preferably 3.50 mass %～5.80 mass % of etching solution total amount.It should be noted that hydrogen peroxide is also referred to as " crossing water ".
<mineral acid>
In order to by the copper dissolution after oxidation, use mineral acid.In order to not affect the baseplate material such as glass, silicon, in addition to alleviate environmental pressure when etching solution discarded, do not use phosphorus compound and fluorine compounds.It addition, do not use hydrochloric acid yet.Can suitably with nitric acid, sulphuric acid.Mineral acid be 0.01 mass % to 0.50 mass % relative to etching solution total amount, be preferably 0.02 mass % to 0.20 mass % scope contain.
<organic acid>
Determination of Organic Acids mainly serves as the effect that the angle of taper in the cross section to the wiring after etching is adjusted.Additionally, it is believed that also have the function of decomposition suppressing hydrogen peroxide to a certain degree.Determination of Organic Acids uses acid organic acid and neutral organic acid combination.Alternatively, it is also possible to the acid organic acid of combination and neutral both organic acid.
As operable organic acid, the aliphatic carboxylic acid of de-carbon number 1～18, carbon number 6～10 aromatic carboxylic acid beyond, it is preferable that the aminoacid etc. of carbon number 1～10 can be listed.
Aliphatic carboxylic acid as carbon number 1～18, it is preferable that can list: formic acid, acetic acid, propanoic acid, lactic acid, glycolic, diglycolic acid, acetone acid, malonic acid, butanoic acid, hydroxybutyric acid, tartaric acid, succinic acid, malic acid, maleic acid, fumaric acid, valeric acid, 1,3-propanedicarboxylic acid, itaconic acid, adipic acid, caproic acid, adipic acid, citric acid, tricarballylic acid, trans-aconitic acid, enanthic acid, sad, lauric acid, myristic acid, Palmic acid, stearic acid, oleic acid, linoleic acid, linolenic acid etc..
Aromatic carboxylic acid as carbon number 6～10, it is preferable that can list: benzoic acid, salicylic acid, mandelic acid, phthalic acid, M-phthalic acid, p-phthalic acid etc..
Additionally, aminoacid as carbon number 1～10, it is preferable that carbamic acid, alanine, glycine, agedoite, aspartic acid, sarcosine, serine, glutamine, glutamic acid, 4-Aminobutanoicacid, imino-diacetic butanoic acid, arginine, leucine, isoleucine, nitrilotriacetic acid etc. can be listed.
In the middle of above-mentioned organic acid, as acid organic acid, it is possible to suitably with glycolic, aspartic acid, glutamic acid, citric acid.Especially by combining use glycolic, aspartic acid, glutamic acid these three simultaneously, it is possible to obtain suitable characteristic.It should be noted that acid organic acid contains 1 mass % to 7 mass % preferably with respect to etching solution total amount.
It addition, when using glycolic, aspartic acid, glutamic acid at the same time, relative to etching solution total amount, it is possible to containing the glycolic of preferably 1 mass % to 5 mass %, more preferably 1.50 mass % to 2.50 mass %.It addition, relative to etching solution total amount, it is possible to containing the aspartic acid of preferably 0.10 mass % to 1.00 mass %, more preferably 0.20 mass % to 0.50 mass %.It addition, relative to etching solution total amount, it is possible to containing the glutamic acid of preferably 0.1 mass % to 1.0 mass %, more preferably 0.60 mass % to 0.90 mass %.
It addition, as neutral organic acid, it is possible to suitably with glycine, alanine or Beta-alanine.It addition, relative to etching solution total amount, it is preferable that containing the neutral organic acid of 0.10 mass % to 3.00 mass %.
It addition, glycolic and other a kind of acid organic acid or a kind of neutral organic acid can be combined beyond above-mentioned.In this case, relative to etching solution total amount, it is possible to containing the glycolic of preferably 1 mass % to 5 mass %, more preferably 1.50 mass % to 2.30 mass %.On the other hand, relative to etching solution total amount, it is possible to acid organic acid containing 0.10 mass % to 1.00 mass %, more preferably 0.3 mass % to 0.7 mass % or neutral organic acid.
<amines>
Amines mainly serves as the pH regulator of etching solution.As amines, it is possible to suitably with the material of carbon number 2～10.nullMore specifically，Preferably can list: ethylenediamine、Trimethylene diamine、Tetra-methylenedimine、1,2-propane diamine、1,3-propane diamine、N,N-dimethyl-1,3-propane diamine、N,N-diethyl-1,3-propane diamine、1,3-diaminobutane、2,3-diaminobutane、Five methylene diamine、2,4-1,5-DAP、Hexamethylene diamine、Heptamethylene diamidogen、Eight methylene diamine diamidogen、Nine methylene diamine、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、Diethylenetriamines、Trien、Tetren、Seven ethylidene eight amine、Nine ethylidene ten amine、The polyamines such as diazabicylo endecatylene；nullEthanolamine、N-methylethanolamine、N methyldiethanol amine、N-ehtylethanolamine、N-amino ethyl ethanolamine、N-propyl group ethanolamine、N-butylethanolamine、Diethanolamine、Triethanolamine、1-amino-2-propanol、N-methyl isopropyl hydramine、N-ethylisopropanolamine、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-butylamine-2-alcohol、N-methyl isophthalic acid-butylamine-2-alcohol、N-ethyl-1-butylamine-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 acid-butylamine-4-alcohol、N-ethyl-1-butylamine-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-octane-4-alcohol、1-aminopropane-2,3-glycol、2-aminopropane-1,3-glycol、Three (methylol) aminomethane、1,2-diaminopropanes-3-alcohol、1,3-diaminopropanes-2-alcohol、2-(2-amino ethoxy) ethanol、2-(2-aminoethylamino) ethanol、The alkanolamines such as diglycolamine，These can be used alone or combine multiple use.In the middle of these, it is particularly preferred to 1-amino-2-propanol.It addition, relative to etching solution total amount, it may be preferred to containing 0.50 mass % to 2.00 mass %, the amines more preferably containing 1.00 mass % to 1.90 mass %.
<peroxide decomposition inhibitor>
In the etching solution of the present invention, as oxidant, utilize hydrogen peroxide.Decompose owing to hydrogen peroxide carries out self, therefore add the decomposing inhibitor suppressing its decomposition.This is the life-span in order to extend etching solution.As main peroxide decomposition inhibitor, outside the urea system stabilizer of hydrogen peroxide such as phenylurea, allylurea, 1,3-dimethyl urea, thiourea, it is preferable that can list: the lower alcohols etc. such as phenyl acetamide, phenylglycol, 1-propanol, 2-propanol.
Especially particularly preferably phenylurea, it is further preferred that preferred compositions uses phenylurea and 1-propanol.When peroxide decomposition inhibitor is phenylurea, relative to etching solution total amount, it is possible to containing preferably 0.05 mass % to 0.20 mass %, more preferably 0.07 mass % to 0.12 mass %.It addition, when being lower alcohol, it may be preferred to containing 0.10 mass % to 2.00 mass %, more preferably 0.80 mass % to 1.20 mass %.
Think that these materials acting on hydrogen peroxide, suppressing the generation of free radical, thus suppressing the decomposition of hydrogen peroxide.It should be noted that relative to etching solution total amount, containing when having more than the phenylurea of 0.20 mass %, phenyl and hydroperoxidation, produce the precipitate different from the reactant of azole compounds and hydrogen peroxide.
<chelating agen>
Cu, Mo are etched and are dissolved in etching solution, thus promoting the decomposition of hydrogen peroxide.Think metallic ion coordination as chelating agen and Cu, Mo, it is prevented that metal ion contacts with hydrogen peroxide, thus suppressing the decomposition of hydrogen peroxide.Therefore, in this manual, it is believed that chelating agen is peroxide decomposition inhibitor.
As chelating agen, it is possible to be suitably used ethylenediaminetetraacetic acid (EDTA), hydroxyethyliminodiacetic acid (HIDA), EDDS (EDDS) this amino carboxylic acid system chelating agen.Relative to etching solution total amount, it may be preferred to containing 0.50 mass % to 1.00 mass %, the chelating agen containing 0.60 mass % to 0.90 mass % preferably.
<polyethers>
Polyethers can become the inhibitor of the etch-rate of Cu.When using polyethers, etching cross section cone angle diminishes, and therefore can be suitable for the adjustment of cone angle.When having sulphuric acid especially as mineral acid, effect is big.As polyethers, it is possible to suitably with Polyethylene Glycol (PEG).Relative to etching solution total amount, it may be preferred to containing 0.10 mass % to 0.50 mass %, the Polyethylene Glycol more preferably containing 0.20 mass % to 0.40 mass %.
<copper ion>
Etching solution for the present invention, it is thus identified that: when etching carries out and contains Cu ion, Mo ion, the increase according to Cu ion concentration, etch-rate changes.For the operating of Etaching device, owing to adding etching concentrated solution in the way of making the change of etch-rate fall into certain allowed band, hydrogen peroxide controls, it is thus preferred to also fall into this allowed band when new liquid.Therefore, the Cu ion of prescribed limit can be contained in etching solution.Specifically, relative to etching solution total amount, containing 500ppm to 7000mmp, preferred 2000ppm to 4000ppm Cu ion time, it is easy to estimate the change of etch-rate, therefore preferably.
<other>
In the etching solution of the present invention, except these compositions, it is possible to interpolation water and normally used various additives in the scope not hindering etching performance.For water, due to for the purpose of Precision Machining, it is therefore desirable for be the material being absent from foreign body.During for pure water or ultra-pure water preferred.
<pH, Wen Du>
The etching solution of the present invention scope preferably in pH2～5, more preferably in pH3～4.5 uses.The etching solution of the present invention can use between 18 DEG C to 40 DEG C.18 DEG C to 35 DEG C can be more preferably, most preferably be 20 DEG C to 32 DEG C.
<preservation>
The etching solution of the present invention can use hydrogen peroxide.Hydrogen peroxide carries out self and decomposes.Therefore containing peroxide decomposition inhibitor in etching solution.But, when stored, it is possible to hydrogen peroxide and other liquid are retained separately.Furthermore it is possible to the raw material except hydrogen peroxide and copper ion (is called " etching solution raw material ".) mix with water and concoct the solution of etching solution raw material.This solution can for the water of the ratio fewer than the ratio of the water of the etching solution shown in aftermentioned embodiment.
The solution of the etching solution raw material that etching solution raw material and water are concocted and obtained will be called " etching concentrated solution ".Etching concentrated solution is compared with etching solution, it does not have hydrogen peroxide, correspondingly volume are few, therefore convenient when preserving, carrying.It addition, in order to reduce volume when preservation, conveying further, it is possible to make " etching highly enriched liquid " of being decreased by the water of " etching concentrated solution ".Etch the etching concentrated solution that highly enriched liquid is the water containing 20% to 70%.Etching concentrated solution contains the water more than 70%.Therefore, etching concentrated solution and hydrogen peroxide can be combined by the etching solution of the present invention, it is also possible to be combined with water and hydrogen peroxide by highly enriched for etching liquid.
<engraving method>
The object of etching solution using the present invention is, molybdenum is lower floor, copper is the multilayer film of layers of copper/molybdenum layer on upper strata.The thickness of the molybdenum layer of lower floor is thinner than the thickness of the copper on upper strata.The thickness of lower floor is set to t0, when the thickness on upper strata is set to t1, be configured to t0/t1 range for 0.01 to 0.2 scope.The scope of t0/t1 depart from this scope, Mo layer blocked up time, it is easy to produce the residue of Mo layer, on the contrary when crossing thin, it does not have play the effect of the basal layer as Cu layer.
Additionally, substrate and the basal layer forming molybdenum layer and layers of copper is not particularly limited, with glass, silicon, non-crystalline silicon for representative, it is also possible to for metal-oxides such as IGZO (amorphous semiconductor being made up of indium (Indium), gallium (Gallium), zinc (Zinc), oxygen (Oxide)).
The etching solution of the present invention is when stored by hydrogen peroxide with etch highly enriched liquid and water and (can be hydrogen peroxide and etch concentrated solution.) be retained separately, it is possibly realized thus preserving.Therefore, time actually used, they are carried out blending to complete etching solution.For the method for blending, as long as the concentration that concentration is regulation of final hydrogen peroxide does not just limit.
One example is shown, concocts the etching concentrated solution mixing etching solution raw material in a certain amount of water and obtain in advance.Hydrogen peroxide is usually made the hydrogen peroxide of the concentration higher than the concentration of hydrogen peroxide of the etching solution of the present invention and supplies.Therefore, with respective ormal weight, hydrogen peroxide and etching concentrated solution are concocted.This operation can also be called the operation of blending multilayer film etching solution.Alternatively, it is also possible to contrast etches the high highly enriched liquid of etching of concentrated solution concentration carries out blending to prepare etching solution with water and hydrogen peroxide.
Copper ion can any stage when etching concentrated solution (or etching highly enriched liquid) with etching solution raw material and water concocting or when concocting etching solution with etching concentrated solution and hydrogen peroxide be mixed into.Of course, it is possible to be added after blending etching solution.It should be noted that when etching concentrated solution and hydrogen peroxide by additional filling in used etching solution, it is possible to it is added without copper ion.This is because etching solution has existed copper ion.
When being etched, as it has been described above, use etching solution in pH2～5, when 18 DEG C to 40 DEG C.Accordingly, it would be desirable to the object of etching is also preheated to this temperature.The method making processed substrate contact with etching solution is not particularly limited.As fountain, from above processed substrate can be sprayed etching solution, it is also possible to for the method making processed substrate be immersed in the pond of etching solution.This operation is properly termed as the operation making multilayer film etching solution contact with processed substrate.
It should be noted that processed substrate is the substrate that state is following, in the folded molybdenum layer (Mo layer) of the layers on substrates such as glass and layers of copper (Cu layer), this stacked film is formed with the pattern of the resist layer formed for pattern.
Embodiment
<explanations of various evaluation methodologys>
For the etching solution of the present invention, (it is called " Mo residue " with the cone angle (°) in cross section of wiring after the etch-rate (nm/min) of copper and molybdenum, etching, the groove of molybdenum layer, the molybdenum layer that remains on substrate.), overetch patience, the presence or absence of precipitate, peroxide decomposition speed (quality %/sky) project be evaluated.
Etch-rate measures as follows.First, by sputtering method on the Silicon Wafer being formed with heat oxide film 100nm, copper forms monofilm with 300nm, molybdenum respectively with the thickness of 150nm.(also with good grounds comparative example is the situation of 35 DEG C to make this copper film and molybdenum film and 30 DEG C.) etching solution contact 20 to 60 seconds.
The 4 terminal 4 sonde method resistrivity meters (MitsubishiChemicalAnalytechCo., Ltd. manufacture: MCP-T610 type) applying constant current mode are used to measure the resistance value of the film before and after etching.Change according to this resistance value calculates Thickness Variation, calculates etch-rate.
Cone angle measures as follows.First, pass through the sputtering method thickness with 20nm on the glass substrate by molybdenum layer film forming, continue the thickness with 300nm thereon by layers of copper film forming, make the multilayer film sample of Cu/Mo.This layers of copper forms the resist being patterned as wiring shape, as the base material of cone angle evaluation.That is, cone angle evaluation base material is formed by the resist layer of the patterning in substrate, molybdenum layer and layers of copper thereon and layers of copper.Make this cone angle evaluation base material be immersed in etching solution during carrying out the time of appropriate etching to be etched.Sample after etching is carried out, makes it dried, cut off wiring portion, observe section.
The observation of section uses SEM (scanning electron microscope, ScanningElectronMicroscope) (Hitachi manufactures: SU8020 type), accelerating potential 1kV, 30000～50000 times when carry out.It should be noted that be appropriately etched to the time started to film printing opacity from etching.The moment of film printing opacity is to be visually confirmed to be.
Section shape is shown in Fig. 1.As shown in Fig. 1 (a), substrate 1 and inclined plane 6 angulation 5 after etching are cone angle (°).When cone angle is 30～60 °, it is judged that for circle (zero).For this angular range outer time, it is judged that for fork (×).It should be noted that " circle " refers to successfully or qualified, " fork " refers to failure or defective.Following evaluation is also identical.It should be noted that in Fig. 1 (a), Mo layer represents with accompanying drawing labelling 3, Cu layer represents with accompanying drawing labelling 2, resist layer represents with accompanying drawing labelling 4.
Shown in the accompanying drawing labelling 10 of the groove of molybdenum layer such as Fig. 1 (b), refer between molybdenum layer 3 and substrate 1 than layers of copper first etched state (back taper).Evaluation can carry out when the evaluation of cone angle simultaneously.For the groove of molybdenum layer, if the 30000 of SEM times are not observed in the observation of 50000 times, be judged as circle (zero), it was observed that be then judged as fork (×).
For Mo residue, in utilizing the observation of optical microscope and SEM, if confirm have residue; be judged to fork (×), confirm then be not judged to circle (zero).It should be noted that optical microscope adopts bright field to observe with the multiplying power of about 100 times and dark field is observed.It addition, SEM observes with 30,000 times to 50,000 times.
For overetch patience (also referred to as " O.E. patience ".), cone angle when having carried out the etching of 2 times of times of appropriate etching required time, the groove of molybdenum layer, Mo residue are observed, are all that " circle " is evaluated and be then judged as circle (zero).Any one judges then to be judged as " pitch (×) " for " fork ".
For the presence or absence of precipitate, after blending etching solution, place the stipulated time (several days) in bottle under room temperature, visually to judge whether produce precipitate in bottle.When producing precipitate, use filter paper filtering etching solution, clean the foreign body remaining on filter paper with pure water so that it is drying at room temperature, obtained crystal, powder body FT-IR (Shimadzu Seisakusho Ltd. manufactures IRaffinity), SEM-EDX (hole field makes manufactured) are analyzed.Be judged as circle (zero) when visual observation is less than precipitate, be visually confirmed to be then be judged as fork (×).
For etching solution, it is important that the cross sectional shape not producing this point of precipitate and wiring is suitable, and in order to extend bath life, the decomposition rate of hydrogen peroxide also becomes important project.Herein as reference, peroxide decomposition speed also serves as assessment item and studies.
For peroxide decomposition speed, titer reagent is set to potassium permanganate, use automatic titration device (MitsubishiChemicalAnalytechCo., Ltd. the GP-200 manufactured), the concentration of hydrogen peroxide of (about 24h) after just concocting etching solution and after the stipulated time is measured.Then, the variable quantity according to concentration of hydrogen peroxide calculates decomposition rate.
When the minimizing amount of the concentration of hydrogen peroxide after 24 hours (a day) is less than 1.0 mass %, be evaluated as circle (zero), be evaluated as when being more than 1.0 mass % fork (×).Even if it should be noted that peroxide decomposition speed is fork, as long as other project is circle, it is also possible to be called the etching solution of the present invention.It should be noted that about whole evaluations, although be unsatisfactory for the condition that circle is evaluated, but when being extremely close to the value of boundary value, it is evaluated as triangle (△).
(embodiment 1)
To by sulphuric acid 0.06 mass %, glycolic 2.50 mass %, aspartic acid 0.44 mass %, glutamic acid 0.87 mass %, Beta-alanine 0.66 mass %, 1-amino-2-propanol 1.61 mass %, phenylurea 0.11 mass %, ethylenediaminetetraacetic acid (later also referred to as " EDTA ".) 0.88 mass % formed etching solution raw material and water 92.87 mass % concoct, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 30 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 1.
(embodiment 2)
To by sulphuric acid 0.07 mass %, glycolic 2.50 mass %, aspartic acid 0.45 mass %, glutamic acid 0.88 mass %, Beta-alanine 0.66 mass %, 1-amino-2-propanol 1.61 mass %, phenylurea 0.11 mass %, ethylenediaminetetraacetic acid 0.88 mass %, Polyethylene Glycol (later also referred to as " PEG ".) 0.33 mass % formed etching solution raw material and water 92.51 mass % concoct, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 30 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 1.
(embodiment 3)
Etching solution raw material and water 92.84 mass % to being formed by nitric acid 0.19 mass %, glycolic 2.05 mass %, aspartic acid 0.44 mass %, glutamic acid 0.90 mass %, Beta-alanine 0.66 mass %, 1-amino-2-propanol 1.94 mass %, phenylurea 0.11 mass %, ethylenediaminetetraacetic acid 0.87 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 30 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 1.
(embodiment 4)
Etching solution raw material and water 92.25 mass % to being formed by nitric acid 0.18 mass %, glycolic 2.55 mass %, aspartic acid 0.45 mass %, glutamic acid 0.91 mass %, Beta-alanine 0.69 mass %, 1-amino-2-propanol 1.66 mass %, phenylurea 0.11 mass %, 1-propanol 1.20 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 30 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 1.
(embodiment 5)
Etching solution raw material and water 92.41 mass % to being formed by sulphuric acid 0.05 mass %, glycolic 2.47 mass %, aspartic acid 0.44 mass %, glutamic acid 0.87 mass %, glycine 1.17 mass %, 1-amino-2-propanol 1.61 mass %, phenylurea 0.11 mass %, ethylenediaminetetraacetic acid 0.87 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 30 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 1.
(embodiment 6)
Etching solution raw material and water 92.73 mass % to being formed by sulphuric acid 0.07 mass %, glycolic 2.46 mass %, aspartic acid 0.44 mass %, glutamic acid 0.87 mass %, Beta-alanine 1.74 mass %, 1-amino-2-propanol 1.58 mass %, phenylurea 0.11 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 30 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 1.
(embodiment 7)
Etching solution raw material and water 95.13 mass % to being formed by sulphuric acid 0.07 mass %, glycolic 2.50 mass %, citric acid 0.61 mass %, 1-amino-2-propanol 1.58 mass %, phenylurea 0.11 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 30 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 1.
(embodiment 8)
Etching solution raw material and water 93.74 mass % to being formed by sulphuric acid 0.07 mass %, glycolic 2.27 mass %, Beta-alanine 0.66 mass %, 1-amino-2-propanol 1.94 mass %, phenylurea 0.11 mass %, ethylenediaminetetraacetic acid 0.87 mass %, polyethers 0.34 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 30 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 1.
<using the comparative example of azole compounds>
(comparative example 1)
Etching solution raw material and water 87.63 mass % to being formed by glycolic 5.62 mass %, glycine 5.20 mass %, 1-amino-2-propanol 1.31 mass %, phenylurea 0.11 mass %, 5-amino-1H-TETRAZOLE 0.13 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 35 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 2.
(comparative example 2)
Etching solution raw material and water 87.68 mass % to being formed by nitric acid 3.91 mass %, glycine 4.33 mass %, 1-amino-2-propanol 3.86 mass %, phenylurea 0.11 mass %, 5-amino-1H-TETRAZOLE 0.11 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 35 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 2.
(comparative example 3)
Etching solution raw material and water 95.45 mass % to being formed by glycolic 2.42 mass %, glycine 1.25 mass %, 1-amino-2-propanol 0.67 mass %, phenylurea 0.12 mass %, 5-amino-1H-TETRAZOLE 0.09 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 35 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 2.
(comparative example 4)
Etching solution raw material and water 94.90 mass % to being formed by glycolic 2.65 mass %, glycine 1.00 mass %, Beta-alanine 0.82 mass %, 1-amino-2-propanol 0.39 mass %, phenylurea 0.12 mass %, 5-amino-1H-TETRAZOLE 0.12 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 35 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 2.
(comparative example 5)
Etching solution raw material and water 94.44 mass % to being formed by nitric acid 0.12 mass %, citric acid 2.45 mass %, 1-amino-2-propanol 2.62 mass %, phenylurea 0.08 mass %, 5-amino-1H-TETRAZOLE 0.29 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 35 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 2.
(comparative example 6)
Etching solution raw material and water 89.83 mass % to being formed by nitric acid 0.08 mass %, glycolic 2.20 mass %, malonic acid 3.98 mass %, lactic acid 1.01 mass %, 1-amino-2-propanol 2.64 mass %, phenylurea 0.12 mass %, 5-amino-1H-TETRAZOLE 0.14 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 35 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 2.
<not using the comparative example of azole compounds>
(comparative example 7)
Etching solution raw material and water 93.72 mass % to being formed by glycolic 2.65 mass %, lactic acid 1.00 mass %, 1-amino-2-propanol 2.52 mass %, phenylurea 0.11 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 35 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 3.
(comparative example 8)
Etching solution raw material and water 93.31 mass % to being formed by malonic acid 3.54 mass %, glycine 1.40 mass %, 1-amino-2-propanol 1.64 mass %, phenylurea 0.11 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 35 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 3.
(comparative example 9)
Etching solution raw material and water 93.21 mass % to being formed by citric acid 3.61 mass %, glycine 1.43 mass %, 1-amino-2-propanol 1.64 mass %, phenylurea 0.11 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 35 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 3.
(comparative example 10)
Etching solution raw material and water 92.05 mass % to being formed by lactic acid 4.73 mass %, glycine 1.39 mass %, 1-amino-2-propanol 1.72 mass %, phenylurea 0.11 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, with liquid temperature 35 DEG C use.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 3.
(comparative example 11)
Etching solution raw material and water 94.43 mass % to being formed by glycolic 2.80 mass %, glycine 1.41 mass %, 1-amino-2-propanol 1.25 mass %, phenylurea 0.11 mass % are concocted, preparation etching concentrated solution.
By 35% hydrogen peroxide and etching concentrated solution mixing, prepare the etching solution that concentration of hydrogen peroxide is 5.30 mass %.And then, add copper sulfate, be prepared in the mode that copper ion concentration is 2000ppm.It addition, liquid temperature is with 35 DEG C of uses.The result of each constituent concentration shared in etching solution entirety and each evaluation item is shown in table 3.
[table 1]
Etching condition
| Project | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Cu concentration | ppm | 2000 | 2000 | 2000 | 2000 | 2000 | 2000 | 2000 | 2000 |
| Temperature | ℃ | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
Evaluation result
| Assessment item | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Cu E.R. | nm/min | 250 | 228 | 260 | 270 | 228 | 214 | 360 | 237 |
| Mo E.R. | nm/min | 32 | 34 | 32 | 43 | 27 | 52 | 75 | 47 |
| Cone angle | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Mo groove | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Mo residue | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| O.E. patience | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Precipitate | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Cross water decomposition speed | Quality %/sky (25 DEG C) | ○ | ○ | ○ | ○ | ○ | △ | △ | △ |
[table 2]
Etching condition
| Project | Unit | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Cu concentration | ppm | 2000 | 2000 | 2000 | 2000 | 2000 | 2000 |
| Temperature | ℃ | 35 | 35 | 35 | 35 | 35 | 35 |
Evaluation result
| Assessment item | Unit | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Cu E.R. | nm/min | 220 | 254 | 214 | 205 | 202 | 293 |
| Mo E.R. | nm/min | 60 | 113 | 127 | 104 | 129 | 114 |
| Cone angle | × (greatly) | × (greatly) | × (greatly) | × (greatly) | × (greatly) | ○ | |
| Mo groove | × | × | × | × | × (greatly) | ○ | |
| Mo residue | ○ | ○ | ○ | ○ | ○ | ○ | |
| O.E. patience | × | × | × | × | × | △ | |
| Precipitate | × | × | × | × | × | × | |
| Cross water decomposition speed | Quality %/sky (25 DEG C) | ○ | ○ | ○ | ○ | ○ | ○ |
[table 3]
Etching condition
| Project | Unit | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 | Comparative example 11 |
| Cu concentration | ppm | 2000 | 2000 | 2000 | 2000 | 2000 |
| Temperature | ℃ | 35 | 35 | 35 | 35 | 35 |
Evaluation result
| Assessment item | Unit | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 | Comparative example 11 |
| Cu E.R. | nm/min | 269 | 563 | 257 | 409 | 257 |
| Mo E.R. | nm/min | 94 | - | 55 | 63 | 66 |
| Cone angle | × (little) | - | × (little) | × (little) | × (little) | |
| Mo groove | ○ | - | ○ | ○ | ○ | |
| Mo residue | × | - | × | × | × | |
| O.E. patience | × | - | × | × | × | |
| Precipitate | ○ | ○ | ○ | ○ | ○ | |
| Cross water decomposition speed | Quality %/sky (25 DEG C) | × | ○ | × | × | × |
<result>
Embodiment 1 to embodiment 8 is the etching solution of the present invention.Owing to not containing azole compounds, between hydrogen peroxide, therefore do not produce reactant, not precipitation portion.Acid organic acid is simultaneously used glycolic, aspartic acid, these 3 kinds of glutamic acid.In the middle of these, so that employ in the etching solution (embodiment 1 to 5) of EDTA or 1 propanol, not only there is no precipitate, and any project of cone angle, Mo groove, Mo residue, O.E. patience be circle evaluation.And then, peroxide decomposition speed, again smaller than 0.1 mass %/sky, obtains desired result.
Further, since overetch patience is good, the time therefore spent from appropriate etching is etched with being able to maintain that good cone angle to the time of 2 times.It addition, for the etching solution of these embodiments, even if the Film Thickness Ratio of Mo and Cu (t0/t1) is different from the situation (20/300) of embodiment, but as long as Film Thickness Ratio is between 0.01 to 0.2, it is also possible to realize the angle of taper of 30 ° to 60 °.
Neutrality organic acid, compared with embodiment 5, is replaced into Beta-alanine from glycine by embodiment 6, and without EDTA.When eliminating EDTA, the decomposition rate (quality %/sky) of hydrogen peroxide has exceeded 1.0 mass %/sky.But, the cross sectional shape of the wiring after etching is good.
Embodiment 7 and 8, for using glycolic and citric acid or glycolic and Beta-alanine, adjusts the etch-rate of Cu and Mo, it is possible to form the example of cone angle with suitable scope.But, peroxide decomposition speed is just over 1.0 mass %/sky.Etching solution accordingly, for the present invention, it may be said that at least contain glycolic as organic acid, and there is hydrogen peroxide, mineral acid, amines and stabilizer of hydrogen peroxide.Furthermore it is possible to containing chelating agen.
Comparative example 1 to comparative example 6 is the example containing azole compounds.As azole compounds, employ 5-amino-1H-TETRAZOLE.As the effect using azole compounds, it is possible to suppress the etch-rate of Cu, and improve the etch-rate of Mo.Therefore, by obtaining the balance with mineral acid, it is possible to control cone angle.
For comparative example 1 to 5, the etch-rate of Mo becomes big, cone angle change is big.Comparative example 6, in order to only improve the etch-rate of copper adjusting sufficient composition, employs the mixing of glycolic, malonic acid, lactic acid.In comparative example 6, cone angle obtains suitable result.But, the etch-rate of Mo is still fast, when carrying out overetch, slightly produces the groove of Mo layer.
Although the composition that comparative example 1 to 6 is so adjustable cone angle, but azole compounds and hydrogen peroxide react and produce precipitate.
Comparative example 7 to 11 is the example not containing azole compounds.As shown in comparative example 1 to 6, have adjusted the etch-rate of Cu and Mo with the combination of mineral acid and azole compounds.Comparative example 7 to 11 is the situation not using azole compounds, it is desirable to adjusted the etch-rate of Cu and Mo by adjustment organic acid and amine.Amine employs 1-amino-2-propanol.
In comparative example 7, employ glycolic and lactic acid as organic acid, but cone angle is little.In comparative example 8, employ malonic acid and glycine, but the etch-rate of Cu is too high, do not leave film.Comparative example 9 to 11 have also been changed neutral organic acid and acid organic acid kind, but the etch-rate of Cu is high, cone angle can not obtain good shape.But, owing to not containing azole compounds, so there is no produce precipitate.
For embodiment, in comparative example 7 to 11 confirm, owing to not using azole compounds, therefore do not produce precipitate.Additionally, compare with comparative example 7 to 11, by using glycolic, aspartic acid and glutamic acid simultaneously, and optionally employ EDTA or lower alcohol 1-propanol to regulate the ratio of the etch-rate of Cu and Mo, it is possible to the suitable cross sectional shape realizing etched part and the etching solution not having precipitate, bath life also to grow.
Industrial applicability
The etching solution of the present invention is regardless of this series products of FPD such as liquid crystal display, plasma scope, organic EL, formed on the substrates such as glass substrate, silicon substrate, non-crystalline silicon substrate, metal oxide substrate or in the situation of the wiring forming the molybdenum layer on the basal layer formed by these materials and layers of copper stacking and obtaining using, it is possible to utilize widely.
Description of reference numerals
1 substrate
2 layers of copper
3 molybdenum layers
4 resists (layer)
5 cone angles
6 inclined planes
10 groove parts
Claims (14)
1. a multilayer film etching solution, described multilayer film comprises layers of copper and molybdenum layer, it is characterised in that it contains hydrogen peroxide, mineral acid, acid organic acid, neutral organic acid, amines and peroxide decomposition inhibitor.
2. multilayer film etching solution according to claim 1, it is characterised in that it does not contain azole compounds, phosphorus compound and fluorine compounds.
3. multilayer film etching solution according to claim 1 and 2, it is characterised in that it is possibly together with amino carboxylic acid system chelating agen.
4. multilayer film etching solution according to any one of claim 1 to 3, it is characterised in that described mineral acid is at least one in sulphuric acid or nitric acid.
5. multilayer film etching solution according to any one of claim 1 to 4, it is characterised in that described acid organic acid comprises glycolic, aspartic acid, these 3 kinds of glutamic acid.
6. multilayer film etching solution according to any one of claim 1 to 5, it is characterised in that described neutral organic acid is any one in glycine and Beta-alanine.
7. multilayer film etching solution according to any one of claim 1 to 6, it is characterised in that described amines is 1-amino-2-propanol.
8. multilayer film etching solution according to any one of claim 1 to 7, it is characterised in that described peroxide decomposition inhibitor is phenylurea or lower alcohol.
9. multilayer film etching solution according to any one of claim 1 to 8, it is characterised in that described amino carboxylic acid system chelating agen is optionally ethylenediaminetetraacetic acid, hydroxyethyliminodiacetic acid, EDDS.
10. multilayer film etching solution according to any one of claim 1 to 9, it is characterised in that it is possibly together with Polyethylene Glycol.
11. multilayer film etching solution according to any one of claim 1 to 10, it is characterised in that it is possibly together with the copper ion of 500～7000ppm.
12. a multilayer film etching concentrated solution, described multilayer film comprises layers of copper and molybdenum layer, it is characterised in that it contains mineral acid, acid organic acid, neutral organic acid, amines, peroxide decomposition inhibitor and water.
13. an engraving method for multilayer film, described multilayer film comprises layers of copper and molybdenum layer, it is characterised in that it includes following operation:
Etching concentrated solution containing mineral acid, acid organic acid, neutral organic acid, amines, peroxide decomposition inhibitor and water is concocted with water and hydrogen peroxide and concocted multilayer film etching solution；And
Described multilayer film etching solution is made to contact with processed substrate.
14. the engraving method of multilayer film according to claim 13, it is characterised in that make the operation that described multilayer film etching solution contacts with processed substrate carry out when being 18 DEG C to 35 DEG C in the scope that pH is 2 to 5 of described multilayer film etching solution, liquid temperature.
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| CN107690488A (en) * | 2016-09-09 | 2018-02-13 | 松下知识产权经营株式会社 | Multilayer film etching solution and etching concentrate and engraving method |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN105765107B (en) | 2017-12-19 |
| TW201533272A (en) | 2015-09-01 |
| JPWO2015075765A1 (en) | 2017-03-16 |
| WO2015075765A1 (en) | 2015-05-28 |
| TWI624565B (en) | 2018-05-21 |
| JP6128404B2 (en) | 2017-05-17 |
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