CN102995021A - Etching solution composition and etching method for copper and copper alloy - Google Patents

Etching solution composition and etching method for copper and copper alloy Download PDF

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CN102995021A
CN102995021A CN2012103305021A CN201210330502A CN102995021A CN 102995021 A CN102995021 A CN 102995021A CN 2012103305021 A CN2012103305021 A CN 2012103305021A CN 201210330502 A CN201210330502 A CN 201210330502A CN 102995021 A CN102995021 A CN 102995021A
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copper
copper alloy
etchant
layer
acid
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高桥秀树
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Kanto Chemical Co Inc
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer

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  • Engineering & Computer Science (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Weting (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Thin Film Transistor (AREA)

Abstract

The invention aims to provide an etching solution composition and an etching method for copper and copper alloy. A metal laminated film containing a copper layer and a copper oxide layer and/or a copper alloy layer is etched by the etching solution composition with good precision, thereby forming an excellent sectional shape, realizing excellent practicability and stability and achieving long service lifetime. The etching solution composition is used to etch the metal laminated film containing the copper layer and the copper oxide layer and/or the copper alloy layer. In addition, the etching solution composition contains 0.1-80 wt% of persulfate solution and/or persulfuric acid solution, 0.1-80 wt% of phosphoric acid and 0.1-50 wt% of nitric acid and/or sulfuric acid and is further added with chloride ions and ammonium ions, thereby making it easy to control the etching rate and the sectional shape.

Description

The etchant of copper and copper alloy and engraving method
Technical field
The present invention relates to employed in the manufacturing of flat-panel monitor etc., carry out etching solution compound for etching to copper and with copper as the metal level press mold of the copper alloy of main component, and the engraving method that uses this etching solution.
Background technology
In the past, use the aluminium film as the meticulous wiring material of liquid crystal indicator, but, driving transistors electrode (driving Move ト ラ Application ジ ス タ Electricity Very) and fine pattern as flat-panel monitor, in order to form live width below several microns, bring into use recently copper or the copper alloy take copper as main component.Thus, applicable dull and stereotyped make, live width is in the etching technique of the copper film below several microns, be restricted so far.
Use in the situation of copper film as electrode, copper is not to use with individual layer, but the metals such as Ti, Mo, MoTi need to be used as adhesion layer, blocking layer, thereby the tack between raising and the glass substrate stops the diffusion of copper.In this case, usually, tested the laminated films such as Ti/Cu/Ti, Cu/Ti, Mo/Cu/Mo, Cu/Mo, MoTi/Cu/MoTi, Cu/MoTi have been used as electrode, also studied the engraving method of various films.
In the patent documentation 1, put down in writing the etching solution of superoxol-acetic acid as the etching solution of the single film of copper or the multiple film of copper molybdenum, but had in hydrogen peroxide-acetic acid over time larger, unmanageable problem of change in concentration and rate of etch.In addition, the liquid time limit of service of superoxol is shorter, in order to make stable performance, need to dissolve in copper in pre-treatment, and the waste liquid after the etching produces gas owing to the decomposition of superoxol, and there is the danger of blast in the container of depositing.And the superoxol system is understood etching glass through being usually used in the in the lump etching of Cu/Ti and Cu/Mo laminated film owing to containing fluorine, so that glass substrate can't recycle, causes material cost to increase.
Employed phosphoric acid-nitric acid-acetic acid can dissolve copper film in the etching of existing aluminium film as wiring material; but immerse easily between protective layer/Cu owing to have liquid; copper etching under the protective layer is carried out easily; and injection flow is higher; therefore the characteristics that rate of etch is lower exist the problem that is difficult to use in jet apparatus.Further, be used for such as laminated films such as Cu/Mo, owing to the poor effect that affects battery of the corrosion potential of laminated film interlayer, thereby the metal of a side very easily dissolves, and is difficult to obtain good pattern form.
Record in the patent documentation 2, it is basic vertical and exist in lower floor in the situation of copper alloy to have a cross-sectional shape at copper for the etching solution of cupric chloride-hydrochloric acid system and iron(ic) chloride-hydrochloric acid system, because rate of etch is higher than copper, etching occurs in lower floor, thereby forms easily the problem such as reverse tapered shapes (being that cone angle is 90 °～180 °).
In addition, in patent documentation 2～patent documentation 5, the etching solution of having discussed by containing persulphate carries out etching to laminated films such as copper individual layer and Cu/Ti or Cu/Mo.
Recently, researched and developed the laminated film that contains copper alloy, as the laminated film that replaces Cu/Ti or Cu/Mo laminated film.Different from the existing layer press mold that uses the dissimilar metals film, these laminated films are laminated films of copper layer and copper alloy layer, have not only the excellent performance as base film layer, and can be to the advantage of each layer film forming in same device of lamination in film process.
But, for the etching solution that the laminated film that contains copper layer and copper oxide layer and/or copper alloy layer carries out efficient etching method and is used for the method, almost study.In the patent documentation 6, disclosed laminated film with copper oxide layer and copper alloy oxide skin, contain superoxide and organic acid etching solution, persulfuric acid or persulphate are disclosed as superoxide.But in containing persulfuric acid or persulphate and organic acid composition, the solubleness of copper significantly reduces under the organic acid impact, causes being difficult to be adjusted to the purpose treatment time.For this reason, the amount that needs to increase persulfuric acid or persulphate promotes solubleness, if but they are carried out increment, etching solution enters between protective layer and copper or the copper alloy easily, protective layer occurs peel off, and is difficult to form pattern.In fact, in the patent documentation 6 among the embodiment of record, preparation because protective layer is peeled off before the copper etching finishes, so can't form pattern after forming of consisting of carrying out the etching of copper/copper alloy substrate by ammonium persulphate, acetic acid and ammonium acetate.Considering and can come treatment substrate with the composition of record in the patent documentation 6, is that copper alloy is the solubleness laminated film higher than copper because substrate is the substrate of the copper alloy/copper alloy of CuMg/CuMgO substrate, therefore can handle together.In addition, consider that copper alloy/copper alloy compares with the substrate of copper/copper alloy, therefore be easy to handle together because solubleness is approximate.As above, because etching characteristic (solubleness) difference in the copper/copper alloy laminated film, even therefore use known etching solution also to can not get the shape of expecting.
Patent documentation 1: TOHKEMY 2004-193620 communique
Patent documentation 2: TOHKEMY 2010-87213 communique
Patent documentation 3: TOHKEMY 2010-265547 communique
Patent documentation 4: No. 3974305 communique of Japanese Patent
Patent documentation 5: Japanese kokai publication hei 11-140669 communique
Patent documentation 6: TOHKEMY 2010-265524 communique
That is, technical problem of the present invention provides in a kind of etching of the laminated film containing copper and copper alloy, the etchant that can control the in the lump etched important factor of laminated film.
Summary of the invention
The present inventor is in order to address the above problem, through repeatedly scrutinizing discovery, for with copper film and the copper alloy take copper as the main component metal level press mold as adhesion layer, blocking layer, phosphoric acid and nitric acid and/or sulfuric acid have been added in use in persulphate and/or persulfate solution etchant carries out etching, can obtain good cross-sectional shape, finish the present invention thereby further study.
That is, the present invention relates to following content.
(1) a kind of etchant, be used for the etching metal laminated film, described metal level press mold contains copper layer and copper oxide layer and/or copper alloy layer (but copper alloy that the copper alloy, copper and the chromium that do not comprise copper alloy, copper and titanium formation that copper and molybdenum form form), and described etchant contains persulfate solution and/or persulfate solution, the phosphoric acid of 0.1～80 % by weight and nitric acid and/or the sulfuric acid of 0.1～50 % by weight of 0.1～80 % by weight.
(2) according to the etchant of above-mentioned (1) record, it is characterized in that persulfate solution is for containing permonosulphuric acid potassium, peroxosulphuric hydrogen potassium (KHSO 5), one or more the aqueous solution in peroxo disulfate acid ammonium or the potassium peroxydisulfate.
(3) according to the etchant of above-mentioned (1) or (2) record, it is characterized in that described persulfate solution and/or persulfate solution contain peroxosulphuric hydrogen potassium (KHSO 5).
According to the etchant of each record in above-mentioned (1)～(3), it is characterized in that (4) described persulfate solution contains permonosulphuric acid potassium, peroxosulphuric hydrogen potassium (KHSO 5), in peroxo disulfate acid ammonium or the potassium peroxydisulfate one or more, and active oxygen is 0.01～5 % by weight.
According to the etchant of each record in above-mentioned (1)～(4), it is characterized in that (5) described etchant does not contain nitric acid.
According to the etchant of each record in above-mentioned (1)～(5), it is characterized in that (6) described etchant further contains the chlorion of 0.00001～30 % by weight.
According to the etchant of each record in above-mentioned (1)～(6), it is characterized in that (7) described etchant further contains the ammonium ion of 0.1～50 % by weight.
(8) according to the etchant of each record in above-mentioned (1)～(7), layer structure, copper alloy and substrate contacts that wherein said metal level press mold is copper/copper alloy or copper alloy/copper/copper alloy.
(9) according to the etchant of each record in above-mentioned (1)～(8), wherein copper alloy is copper-magnesium-aluminium or copper-magnesium-aluminum oxide.
(10) according to the etchant of each record in above-mentioned (1)～(9), wherein said etchant is used at flat-panel monitor etching driving transistors electrode.
(11) a kind of engraving method, described engraving method is the engraving method that contains the metal level press mold of copper layer and copper oxide layer and/or copper alloy layer (but copper alloy that the copper alloy, copper and the chromium that do not comprise copper alloy, copper and titanium formation that copper and molybdenum form form), and described engraving method comprises that the etchant of each record in use above-mentioned (1)～(10) carries out etched operation.
(12) engraving method of putting down in writing according to above-mentioned (11), layer structure, copper alloy and substrate contacts that wherein said metal level press mold is copper/copper alloy or copper alloy/copper/copper alloy.
(13) according to the engraving method of above-mentioned (11) or (12) record, wherein copper alloy is copper-magnesium-aluminium or copper-magnesium-aluminum oxide.
(14) according to the engraving method of each record in above-mentioned (11) to (13), wherein, described method is used at flat-panel monitor etching driving transistors electrode.
According to said structure, engraving method of the present invention for copper and copper oxide and/the metal level press mold of copper alloy take copper as main component, even in the metallic film fine pattern situation of live width 0.5～5 μ m, also can carry out etching and processing with good precision.Only use the words of persulphate and/or persulfate solution, owing to cross-sectional shape becomes the shaggy problem in vertical configuration, cross section and the low problem that exists lower floor to become easily outstanding shape of copper alloy solubleness of lower floor, and in etchant of the present invention, the interaction of persulphate and/or persulfate solution, phosphoric acid and nitric acid and/or sulfuric acid can be etched to the metal level press mold that contains copper layer and copper oxide layer and/or copper alloy layer good positive taper (being that cone angle is 0 °～90 °).
In addition, rate of etch and cone angle can be controlled, the high etching of inner evenness of lateral erosion and residue generation can be carried out to suppress.
Further, adopt impregnated or jet-type also can obtain good cross-sectional shape, in the situation of jet-type, along with injection flow increases, rate of etch raises, and therefore practicality easy to use is excellent.
Especially, copper alloy is the laminated film of copper-magnesium-aluminium (Cu-Mg-Al) or copper-magnesium-aluminum oxide (Cu-Mg-Al-O), viewpoint from tack and block, what the present inventor paid close attention to most is the copper laminated film, utilizes etchant of the present invention to form meticulous pattern by etching thereby made a good job of.
Description of drawings
Fig. 1 is the SEM photo in the substrate cross section after the etch processes among the embodiment 1～8;
Fig. 2 is the SEM photo in the substrate cross section after the etch processes among the embodiment 9～19;
Fig. 3 is the SEM photo in the substrate cross section after the etch processes among the embodiment 20～36;
Fig. 4 is the SEM photo in the different two kinds of substrate cross sections of thickness after the etch processes among the embodiment 54;
Fig. 5 is the SEM photo in the substrate cross section after the etch processes among the embodiment 55～58;
Fig. 6 is the SEM photo in the substrate cross section after the etch processes among the embodiment 59～62;
Fig. 7 is the SEM photo in the substrate cross section after the etch processes among the embodiment 63～66;
Fig. 8 is the SEM photo in the substrate cross section after the etch processes in embodiment 67 and the comparative example 1.
Embodiment
An aspect of of the present present invention is a kind of etchant for the etching metal laminated film, described metal level press mold contains copper layer and copper oxide layer and/or copper alloy layer (but copper alloy that the copper alloy, copper and the chromium that do not comprise copper alloy, copper and titanium formation that copper and molybdenum form form), and described etchant contains persulfate solution and/or persulfate solution, the phosphoric acid of 0.1～80 % by weight and nitric acid and/or the sulfuric acid of 0.1～50 % by weight of 0.1～80 % by weight.
Copper alloy among the present invention is take copper as main component and contains the copper alloy of copper and any metal, comprises the copper alloy oxide compound.Preferably, contain the above copper of 80 atomic percents, can enumerate Cu-Ca, Cu-Mg, Cu-Ca-O, Cu-Mg-O, Cu-Al, Cu-Zr, Cu-Mn, Cu-Ni-B, Cu-Mn-B, Cu-Ni-B, Cu-Si, Cu-Mg-B, Cu-Ti-B, Cu-Mo-B, Cu-Al-B, Cu-Si-B, Cu-Mg-Al, Cu-Mg-Al-O etc.But the copper alloy that the copper alloy, copper and the chromium that do not comprise copper alloy, copper and titanium formation that copper and molybdenum form form.Particularly Cu-Mg-Al and Cu-Mg-Al-O can access good shape and preferred.
Metal level press mold among the present invention contains copper layer and copper oxide layer and/or copper alloy layer (but copper alloy that the copper alloy, copper and the chromium that do not comprise copper alloy, copper and titanium formation that copper and molybdenum form form).Lamination typically is two-layer substrate, but is also can carry out in the lump etching more than three layers the time.Typically, two-layer substrate is the layer structure of copper/copper alloy, and three laminar substrates are the layer mechanism of copper alloy/copper/copper alloy, are the layer structure of copper alloy and substrate contacts arbitrarily.Here, substrate is not limited to this, can contain glass, silicon, pottery, polyimide etc. and be desirably in all material that its surface forms pattern as insulating material or semi-conductor, is preferably glass or silicon.
Among the present invention, persulfate solution refers to contain the aqueous solution of persulphates such as permonosulphuric acid salt and/or peracetic dithionite, and persulphate can be enumerated permonosulphuric acid potassium, peroxosulphuric hydrogen potassium (KHSO 5), permonosulphuric acid sodium (NaHSO 5), peroxo disulfate acid ammonium ((NH 4) 2S 2O 8), potassium peroxydisulfate (K 2S 2O 8), sodium peroxydisulfate (Na 2S 2O 8) etc., but be not limited to this.
Based on the viewpoint of solubleness, persulfate solution preferably contains permonosulphuric acid potassium, peroxo disulfate acid ammonium ((NH 4) S 2O 8) and peroxosulphuric hydrogen potassium (KHSO 5) the aqueous solution.
Term " permonosulphuric acid potassium " is usually used in the business transaction, is used for expression in this specification sheets and mixes triple salt 2KHSO 5KHSO 4K 2SO 4Term " KHSO 5" be used in particular in this manual representing peroxosulphuric hydrogen potassium.
Permonosulphuric acid potassium is known with trade(brand)name オ キ ソ Application (permonosulphuric acid potassium), and the stability of solution of this persulphate is high, and this point is especially preferred.
Among the present invention, persulfate solution refers to contain permonosulphuric acid potassium, peroxosulphuric hydrogen potassium (KHSO 5), permonosulphuric acid sodium (NaHSO 5), peroxo disulfate acid ammonium ((NH 4) 2S 2O 8), potassium peroxydisulfate (K 2S 2O 8), sodium peroxydisulfate (Na 2S 2O 8) etc. persulphate, active oxygen is 0.01～5 % by weight, be preferably 0.3～3 % by weight, the aqueous solution of 0.5～2 % by weight more preferably.
Have 5.2% theoretical active o content as the permonosulphuric acid potassium of solid, commercially available solid triple salt has about 4.7% typical activity oxygen level.Recognize that the purity of commercially available permonosulphuric acid potassium is 95～98% owing to the change in a small amount of impurity, a small amount of additive and the manufacturing processed.
" active oxygen " is defined as the oxygen amount that exceeds in the permonosulphuric acid potassium triple salt that forms corresponding hydrosulfate requisite oxygen amount.This can calculate with percentage by the reaction formula that permonosulphuric acid potassium decomposes.
Reaction formula 1
KHSO 5→KHSO 4+[O]
Active oxygen %=(weight of [O] * 100)/KHSO 5Weight
In the formula, [O] for since shown in the free oxygen of decomposition.When the reaction formula that is applied to provide, the weight that the weight of KHSO5 is used the sample of impurity material replaces.Certainly, active oxygen can be by multiple reaction, and the displacement of the iodine that is for example produced by quantitative potassiumiodide is determined.
(mensuration of active oxygen)
The measuring method of active oxygen carries out according to Japanese Unexamined Patent Application Publication 2009-539740, determines with the iodometric titration of standard.With sample to be analyzed with cold deionized water dilute, acidifying, process with potassiumiodide, with stdn 0.1N thiosulfuric acid sodium reagent, estimate terminal point by Starch Indicator and carry out titration.Active o content is calculated as follows.
Active oxygen %=(mL Titrating solution* equivalent concentration Titrating solution* 0.8)/(g Sample)
Equally, KHSO 5The concentration of % can be by following calculating.
KHSO 5%=active oxygen %/0.105
The concentration of persulphate and/or persulfate solution is 0.1～80 % by weight, is preferably 5～35 % by weight.As long as in above-mentioned scope, then can still be less than or greater than in the situation of above-mentioned scope by controlling respectively rate of etch and lateral erosion with the combination of other compositions, rate of etch becomes extremely low or high state, thereby is difficult to control.
Etchant of the present invention contains phosphoric acid.The concentration of phosphoric acid is 0.1～80 % by weight, be preferably 5～50 % by weight.Phosphoric acid is less than or greater than in the situation of above-mentioned scope, the inner evenness variation, and it is large that lateral erosion becomes easily, only control difficulty during other compositions.Can contain in nitric acid or the sulfuric acid any one or both contain.The etching solution that preferably contains sulfuric acid.Contain that concentration adds up to 0.1～50 % by weight in the situation of nitric acid and sulfuric acid, be preferably and contain nitric acid 1～20 % by weight and sulfuric acid is 1～30 % by weight.Only contain in the situation of sulfuric acid, the concentration of sulfuric acid is 0.1～50 % by weight, is preferably 1～30 % by weight.
In an embodiment of the invention, etchant of the present invention does not contain nitric acid.The composition of persulfate solution, phosphoric acid and sulfuric acid is compared with the composition of persulfate solution, phosphoric acid and nitric acid, and sulfate ion is more, therefore can improve the stability of solution of the negatively charged ion of persulphate.In addition, also have such advantage, even persulfate solution is when alkalescence, when adding nitric acid, the change of rate of etch is less, but because high speed when adding phosphoric acid, low speed when adding sulfuric acid by regulating the amount of phosphoric acid and sulfuric acid, can be controlled rate of etch easily.
In the embodiments of the present invention, etchant of the present invention can also contain chlorion.Thereby the compound that chlorion can be by adding water-soluble rear easy generation chlorion or hydrochloric acid etc. are present in the etchant.Produce the compound of chlorion, can enumerate zinc chloride, zinc ammonium chloride, aluminum chloride, ammonium chloride, cobalt chloride (II), cupric chloride (II), Palladous chloride, isobutyl chloride, isopropyl chloride, indium chloride (III), vinylchlorid, oleoyl chloride, Repone K, calcium chloride, silver chloride, chromium chloride (II), cobalt chloride (II), choline chloride 60, zirconium chloride (IV), mercury chloride (I), tin chloride (IV), tin chloride (II), tin chloride (VI), strontium chloride, cesium chloride, Cerium II Chloride (III), tungsten chloride (VI), tantalum chloride (V), titanium chloride (IV), titanium chloride (III), iron(ic) chloride (II), iron(ic) chloride (III), etamon chloride, cupric chloride (I), cupric chloride (II), sodium-chlor, lead chloride (II), nickelous chloride (II), platinum chloride (II), platinum chloride (IV) potassium, bariumchloride, Palladous chloride (II), methylene dichloride, ethylene dichloride, lithium chloride etc.Particularly based on the viewpoint of the wettability of the stability of solution in the acidic solution and retrofit section and preferred hydrochloric acid.Found that chlorion has contribution especially to the dissolution rate of copper alloy, can control speed and cone angle.In addition, the translational speed of chlorion in the aqueous solution is high, therefore promotes the uniform dissolution on machined object surface, improves inner evenness, and also suppresses lateral erosion.
The concentration of chlorion can suitably be set according to film kind and the thickness of copper alloy, can be for 0.00001～30 % by weight, be preferably 0.00003～2 % by weight, 0.00003～0.05 % by weight more preferably, but be not limited to this.Chlorion does not almost improve the effect of inner evenness during less than above-mentioned scope, and during greater than above-mentioned scope, the dissolution rate of copper alloy is faster than copper, therefore has the tendency of cross-sectional shape variation.Further, generate easily the residue that is considered to cuprous chloride.This thinks because chlorine and copper surface reaction form the cuprous chloride that is difficult to dissolve on the copper surface, and this cuprous chloride hinders etching.Yet etchant of the present invention can suppress to generate cuprous chloride by adding ammonium ion, can control the generation of residue.
The compound that ammonium ion can produce easily by being added on water dissolution ammonium ion is present in the etchant.Generate the compound of ammonium ion, can enumerate Secondary ammonium phosphate, amidosulphuric acid, zinc ammonium chloride, ammonium chloride, ammonium chloride cobalt (II), ammonium chloride copper (II), ammonium chloride palladium (II), etamon chloride, tetrabutylammonium chloride, 4-propyl ammonium chloride, hydroxylammonium chloride, the ammonium perchlorate, the periodic acid ammonium, ammonium formiate, ammonium citrate, FAC (III), citric acid one ammonium, Triammonium citrate, diammonium hydrogen citrate, ironic citrate (III) ammonium, ammonium dihydrogen citrate, ammonium acetate, the tetraboric acid ammonium, brometo de amonio, ammonium oxalate, ammonium binoxalate, ironic oxalate (III) ammonium, ammonium tartrate, ammonium nitrate, cerium ammonium nitrate (IV), tetraethyl ammonium hydroxide, TBAH, TPAOH, Tetramethylammonium hydroxide, bicarbonate of ammonia, volatile salt, ammonium thiosulfate, the trifluoroacetic acid ammonium, DL-Lactic acid ammonium salt, ammonium bifluoride, ammonium borate, ammonium iodide, ammonium sulfate, aluminium ammonium sulfate, chromium ammonium suplhate (III), cobaltous ammonium sulfate (II), ammonium sulfate iron (II), ammonium sulfate iron (III), Tetraamminecopper Sulfate (II), nickel ammonium sulfate (II), ammonium sulfate magnesium, ammonium sulfate manganese (II), monoammonium phosphate, triammonium phosphate, ammonium hydrogen phosphate is received and primary ammonium phosphate etc., consider preferably phosphoric acid ammonium dihydrogen and Secondary ammonium phosphate from the viewpoint of solubleness especially.The concentration of ammonium ion can suitably be set according to the concentration of the film kind of copper alloy and thickness and persulfate solution and nitric acid, sulfuric acid, chlorion, is 0.1～50 % by weight, is preferably 1～5 % by weight, but be not limited to this.The concentration of ammonium ion is during less than above-mentioned scope, and the residue that causes when adding chlorion generates and suppresses, the control of copper alloy dissolution rate is become difficult, and when greater than above-mentioned scope being, the dissolution rate of copper alloy is excessively low, the easy variation of cross-sectional shape.
By adjusting the concentration of chlorion and ammonium ion, can control the dissolution rate of copper and copper alloy, utilize this point can easily control cone angle.The scope of cone angle is 20～100 degree, preferred 30～60 degree.
Further, chlorion and ammonium ion are effective especially in the etching of three laminar substrates.Namely; in the situation of three laminar substrates; liquid is to immersing between protective layer/copper alloy significantly; compare the problem that exists cone angle to diminish with two-layer substrate; but by adding chlorion and ammonium ion; the liquid that can adjust between protective layer/copper alloy and between copper alloy/glass immerses, and can control the cone angle of three laminar substrates.
In the etchant of the present invention, to carry out etched wettability in order improving, can further to contain one or more tensio-active agent.Tensio-active agent is preferably anionic species or nonionic class.
The etchant of the application of the invention does not use superoxol or fluorine cpd and carries out simple etch processes, can carry out safely the high precision etching thus.In addition, do not need as the composition that uses aqueous hydrogen peroxide solution, before processing substrate, dissolve in copper for the rate of etch that makes copper stablizes.Therefore further, do not contain organic acid and can carry out etching yet, need not to consider that protective layer the problem such as peels off.
Etchant of the present invention also can use persulphate and/or persulfate solution, phosphoric acid, nitric acid, sulfuric acid, chlorion and ammonium ion preparation bulking liquor, for example for the rate of descent of rate of etch, even only add the persulfate solution of necessary amount, also can prolong the time limit of service of solution, but according to circumstances, add simultaneously other compositions, then can further prolong the time limit of service of solution.Thus, can reduce use cost.
Another aspect of the present invention relates to a kind of engraving method, described engraving method is the engraving method of the metal level press mold that contains copper layer and copper oxide layer and/or copper alloy layer (but do not comprise copper alloy, copper and chromium formation that copper alloy that copper and molybdenum form, copper and titanium form copper alloy), and described engraving method comprises that the etchant that use contains the sulfuric acid of the nitric acid of the phosphoric acid of the persulfate solution of 0.1～80 % by weight and/or persulfate solution, 0.1～80 % by weight and 0.1～50 % by weight and/or 0.1～50 % by weight carries out etched operation.
According to engraving method of the present invention, the difference owing to the dissolution rate Yin Wendu of copper and copper alloy so utilize this point to change temperature, can be controlled cone angle.The viewpoint of the temperature condition that preferred temperature can be set based on etching system is 20～80 ℃, and more preferably temperature is 25～40 ℃.
Etchant of the present invention and engraving method are containing new copper alloy, are being in the laminated film of copper-magnesium-aluminum alloy and/or copper-magnesium-aluminum oxide alloy, demonstrate excellent especially etching characteristic.Here, in copper-magnesium-aluminum alloy, be preferably by 0.1～10.0 atom %Mg, 0.1～10.0 atom %Al, remaining Cu and inevitably the target that forms of impurity carry out sputter and the alloy that obtains, be the Cu alloy film that wiring film is used.The alloy of copper-magnesium-aluminum oxide alloy for obtaining by the aforementioned target of sputter under 0.1～20% oxygen partial pressure condition.The reduction-oxidation film owing to the H plasma treatment that carries out in the TFT manufacturing processed in the manufacturing processed of flat-panel monitor can not occur in the film that copper-magnesium-aluminum oxide alloy forms, thus the problem (ULVAC TECHNICAL JOUNAL No.71 2009 P24～28 pages) that tack worsens.
In an embodiment of the invention, etchant of the present invention and engraving method relate to etchant and the engraving method that is used for etching driving transistors electrode in flat-panel monitor.
Embodiment
Below enumerate embodiment and comparative example and describe the present invention in detail, but the present invention can suitably change in the scope that does not change its purport not owing to these embodiment are subject to any restriction.
Embodiment 1～53
Right on the glass substrate The Cu alloy (Cu-Mg-Al) of thickness,
Figure BDA00002111911400112
The Cu of thickness carries out after the film forming, forms the protective layer pattern, floods with 1.5 times the time of just etching time under 30 ℃ of fluid temperatures in the etching solution shown in table 1～4.Then, washing, drying, assessment residue.And persulfate solution uses the LD100 of E.I.Du Pont Company's production (with KHSO 5Solution for main component).
The result is shown in table 1～4.And Fig. 1～Fig. 3 shows respectively the SEM description of table 1～table 3.
[table 1]
The evaluation result of various compositions [J.E.T. * 1.5]
The Cu/CuMgAl substrate
Figure BDA00002111911400113
[table 2]
The evaluation result of various compositions [J.E.T. * 1.5]
The Cu/CuMgAl substrate
Figure BDA00002111911400121
[table 3]
The evaluation result of various compositions [J.E.T. * 1.5]
The Cu/CuMgAl substrate
[table 4]
The evaluation result of various compositions [J.E.T. * 1.5]
The Cu/CuMgAl substrate
Figure BDA00002111911400131
Fixed L D100 (KHSO 5) concentration, confirm the cross-sectional shape of the Cu/CuMgAl substrate when nitric acid or sulfuric acid concentration and phosphoric acid concentration change, the side etching quantity that depends on various concentration changes, and therefore finds can control side etching quantity by with each concentration optimization.For side etching quantity, when substrate film thickness is below 10 times, can take full advantage of, preferred below 7～4 times, more preferably below 3 times, especially preferred below 2 times.In addition, because rate of etch also changes simultaneously, therefore by adjusting the concentration of phosphoric acid and nitric acid and/or sulfuric acid, can control simultaneously side etching quantity and rate of etch.
Embodiment 54
Film forming on glass substrate respectively The Cu alloy (Cu-Mg-Al) of thickness,
Figure BDA00002111911400133
The substrate of the Cu of thickness and on glass substrate film forming
Figure BDA00002111911400134
The Cu alloy (Cu-Mg-Al) of thickness,
Figure BDA00002111911400135
Form the protective layer pattern on the substrate of the Cu of thickness, in the etching solution shown in the table 5 fluid temperature be under 30 ℃, 40 ℃, 50 ℃ 1.5 times time with the just etching time flood.Then, washing, drying is estimated residue.And persulfate solution uses the LD100 of E.I.Du Pont Company's production (with KHSO 5Solution for main component).
The results are shown in table 6, the SEM photo of table 6 the results are shown in Fig. 4.
[table 5]
Form
LD100 (% by weight) HNO 3(% by weight) H 3PO 4(% by weight)
Embodiment 54 11.7 3.2 8.2
[table 6]
The evaluation result of various compositions [J.E.T. * 1.5]
The Cu/CuMgAl substrate
Figure BDA00002111911400141
Use two kinds of different substrates of thickness, confirm the cross-sectional shape when strength of solution changes, confirmed anyly all along with temperature rises, cone angle rises.In addition, confirmed Cu (
Figure BDA00002111911400142
)/CuMgAl (
Figure BDA00002111911400143
) substrate than Cu (
Figure BDA00002111911400144
)/CuMgAl (
Figure BDA00002111911400145
) substrate, the variation range of cone angle is larger.The major cause that cone angle changes is that the dissolution rate of Cu and CuMgAl changes, and particularly CuMgAl is higher to the dependency of solution temperature.In addition, also relevant with the thickness of substrate, the thickness of CuMgAl is thinner, and is faster from the dissolving of lower floor, large on the impact of cone angle, and its controllable scope is also become large.
Embodiment 55～58
Right on the glass substrate
Figure BDA00002111911400146
The Cu alloy (Cu-Mg-Al) of thickness,
Figure BDA00002111911400147
The Cu of thickness carries out after the film forming, forms the protective layer pattern, and is as shown in table 7, makes the etching solution of embodiment 55 be alkalescence, estimates cross-sectional shape and residue when adding hydrochloric acid.And, under 30 ℃ of fluid temperatures, flood with 1.5 times the time of just etching time.In addition, persulfate solution uses the LD100 of E.I.Du Pont Company's production (with KHSO 5Solution for main component).
The results are shown in table 8, the SEM photo of table 8 the results are shown in Fig. 5.
[table 7]
Various compositions
Figure BDA00002111911400151
[table 8]
The evaluation result of various compositions [J.E.T. * 1.5]
The Cu/CuMgAl substrate
Figure BDA00002111911400152
Cross-sectional shape when the composition of affirmation embodiment 55 changes concentration of hydrochloric acid under alkaline condition has confirmed that cone angle rises along with temperature rises.In addition, find to suppress side etching quantity along with concentration of hydrochloric acid rises.
Here, chlorion and the reactivity ratio of CuMgAl and the reactive height of Cu can be controlled cone angle or cross-sectional shape thus.In addition, think because chlorion is high in the translational speed of the aqueous solution, promote the uniform dissolution on machined object surface, improve inner evenness, thereby can suppress lateral erosion.
Embodiment 59～62
Right on the glass substrate
Figure BDA00002111911400153
The Cu alloy (Cu-Mg-Al) of thickness,
Figure BDA00002111911400154
The Cu of thickness carries out after the film forming, forms the protective layer pattern, and is as shown in table 9, makes the etching solution of embodiment 59 be alkalescence, estimates cross-sectional shape and residue when adding hydrochloric acid.In addition, when estimating interpolation hydrochloric acid, also add Secondary ammonium phosphate evaluation.And, under 30 ℃ of fluid temperatures, flood with 1.5 times the time of just etching time.In addition, persulfate solution uses the LD100 of E.I.Du Pont Company's production (with KHSO 5Solution for main component).The results are shown in table 10, the SEM photo of table 10 the results are shown in Fig. 6.
[table 9]
Various compositions
Figure BDA00002111911400161
[table 10]
The evaluation result of various compositions [J.E.T. * 1.5]
The CuMgAl/CuMgAl substrate
Side etching quantity (μ m) Cone angle (°) Conical in shape Residue
Embodiment 59 0.49 20 Positive taper Nothing
Embodiment 60 0.52 15 Positive taper Nothing
Embodiment 61 0.55 15 Positive taper Nothing
Embodiment 62 0.69 55 Positive taper Nothing
Embodiment 63～66
Right on the glass substrate
Figure BDA00002111911400162
The Cu alloy (Cu-Mg-Al) of thickness,
Figure BDA00002111911400163
The Cu of thickness carries out after the film forming, forms the protective layer pattern, and is as shown in table 11, makes the etching solution of embodiment 63 be alkalescence, estimates cross-sectional shape and residue when adding hydrochloric acid.In addition, when estimating interpolation hydrochloric acid, also add Secondary ammonium phosphate evaluation.And, under 30 ℃ of fluid temperatures, flood with 1.5 times the time of just etching time.In addition, persulfate solution uses the LD100 of E.I.Du Pont Company's production (with KHSO 5Solution for main component).The results are shown in table 12, the SEM photo of table 12 the results are shown in Fig. 7.
[table 11]
Various compositions
Figure BDA00002111911400171
[table 12]
The evaluation result of various compositions [J.E.T. * 1.5]
The CuMgAl/CuMgAl substrate
Side etching quantity (μ m) Cone angle (°) Conical in shape Residue
Embodiment 63 0.49 15 Positive taper Nothing
Embodiment
64 0.50 15 Positive taper Nothing
Embodiment 65 1.42 20 Positive taper Nothing
Embodiment 66 1.50 25 Positive taper Nothing
Than two-layer (Cu/CuMgAl) substrate, the cone angle of three layers of (CuMgAl/Cu/CuMgAl) substrate diminishes easily.Therefore, it is few to carry out side etching quantity, can keep the etching of positive taper, but only utilizes the interpolation concentration of hydrochloric acid to be difficult to control accurately cone angle.In a way, can cross-sectional shape be changed by increasing concentration of hydrochloric acid, if concentration of hydrochloric acid is too high, then generate the residue of thinking cuprous chloride at substrate surface easily.For this reason, the concentration of control hydrochloric acid and Secondary ammonium phosphate and adding has confirmed to suppress the generation of residue, and keeping positive taper ground carries out the larger etching of cone angle, thereby can control cone angle.
Embodiment 67 and comparative example 1
Right on the glass substrate The Cu alloy (Cu-Mg-Al) of thickness,
Figure BDA00002111911400173
The Cu of thickness carries out after the film forming, forms the protective layer pattern, uses the etching solution of table 13 to estimate etching.Test method is, uses two kinds of dip test and ejection tests, and dip test is substrate is flooded in beaker and to carry out etching, and ejection test is to carry out etching with the atomized spray etching solution on substrate.Fluid temperature is 30 ℃, processes with 1.5 times time of just etching time, then, and washing, drying is estimated residue.And persulfate solution uses the LD100 of E.I.Du Pont Company's production (with KHSO 5Solution for main component).
The results are shown in table 14, the SEM photo of table 14 the results are shown in Fig. 8.
[table 13]
Various compositions
Figure BDA00002111911400181
[table 14]
The evaluation result of various compositions [J.E.T. * 1.5]
The Cu/CuMgAl substrate
Figure BDA00002111911400182
Use contains in the comparative example 1 of the embodiment 67 of persulphate, phosphoric acid and sulfuric acid and phosphoric acid+nitric acid+acetic acid, carries out dip test and ejection test.Judge, in the dip test, the cross-sectional shape of arbitrary composition all be positive taper without residue, obtain good result, but in the ejection test, only the cross-sectional shape of comparative example 1 is dual tapered, become the shape (representing with flechette-type) as the front end of arrow.
Its reason is thought because the solubility property of two kinds of solution is different.For the etching solution of the present invention that contains persulphate, phosphoric acid and sulfuric acid, in the beaker test, along with stirring velocity rises, the rate of etch of Cu also rises; But in phosphoric acid+nitric acid+acetic acid, along with stirring velocity rises, there is the tendency that reduces in the rate of etch of Cu.Because the stirring velocity of beaker test shows the tendency identical with the flow of ejection test, thus in phosphoric acid+nitric acid+acetic acid, along with injection flow rises, the rate of etch reduction that becomes.In addition, the flow of ejection test more is difficult to control than the stirring velocity of beaker test, has the tendency that flow uprises (being difficult to reduce) easily.
Thus, in the composition of comparative example 1, only spraying dissolves hardly.By inference, although the liquid of spraying accumulates on the substrate and might dissolve, because it is higher than the rate of etch of spraying to accumulate in the rate of etch of the liquid on the substrate, so the lower floor that contacts with the liquid that accumulates dissolves first than the upper strata, become the cross-sectional shape of flechette-type.
In addition, in the ejection test of comparative example 1, also exist the substrate end to produce easily the problems such as residue, for example, even can set the flow of jet apparatus attenuates, because span of control is very little, so be difficult to use.In contrast to this, the composition that embodiment is used no matter be that dip test or ejection test do not need to set careful condition, can be prepared the composition of sening as an envoy to cross-sectional shape well and not producing residue.

Claims (14)

1. etchant, be used for the etching metal laminated film, described metal level press mold contains copper layer and copper oxide layer and/or copper alloy layer, described copper alloy layer does not comprise the copper alloy that copper alloy, copper and the chromium of copper alloy, copper and titanium formation that copper and molybdenum form form, and described etchant contains persulfate solution and/or persulfate solution, the phosphoric acid of 0.1～80 % by weight and nitric acid and/or the sulfuric acid of 0.1～50 % by weight of 0.1～80 % by weight.
2. etchant according to claim 1 is characterized in that, described persulfate solution is one or more the aqueous solution that contains in permonosulphuric acid potassium, peroxosulphuric hydrogen potassium, peroxo disulfate acid ammonium or the potassium peroxydisulfate.
3. etchant according to claim 1 and 2 is characterized in that, described persulfate solution and/or persulfate solution contain peroxosulphuric hydrogen potassium.
4. etchant according to claim 1 and 2, it is characterized in that, described persulfate solution contains one or more in permonosulphuric acid potassium, peroxosulphuric hydrogen potassium, peroxo disulfate acid ammonium or the potassium peroxydisulfate, and active oxygen is 0.01～5 % by weight.
5. etchant according to claim 1 and 2 is characterized in that, described etchant does not contain nitric acid.
6. etchant according to claim 1 and 2 is characterized in that, described etchant further contains the chlorion of 0.00001～30 % by weight.
7. etchant according to claim 1 and 2 is characterized in that, described etchant further contains the ammonium ion of 0.1～50 % by weight.
8. etchant according to claim 1 and 2, wherein the metal level press mold is layer structure, copper alloy and the substrate contacts of copper/copper alloy or copper alloy/copper/copper alloy.
According to claim 1 and 2 in each described etchant, wherein copper alloy is copper-magnesium-aluminium or copper-magnesium-aluminum oxide.
10. etchant according to claim 1 and 2, wherein said etchant is used at flat-panel monitor etching driving transistors electrode.
11. engraving method, described engraving method is the engraving method that contains the metal level press mold of copper layer and copper oxide layer and/or copper alloy layer, described copper alloy layer does not comprise the copper alloy that copper alloy, copper and the chromium of copper alloy, copper and titanium formation that copper and molybdenum form form, and described engraving method comprises that each described etchant carries out etched operation in the right to use requirement 1 to 10.
12. engraving method according to claim 11, wherein the metal level press mold is layer structure, copper alloy and the substrate contacts of copper/copper alloy or copper alloy/copper/copper alloy.
13. according to claim 11 or 12 described engraving methods, wherein copper alloy is copper-magnesium-aluminium or copper-magnesium-aluminum oxide.
14. according to claim 11 or 12 described engraving methods, wherein, described method is used at flat-panel monitor etching driving transistors electrode.
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