CN1847457A - Metal selective etching liquid - Google Patents

Metal selective etching liquid Download PDF

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Publication number
CN1847457A
CN1847457A CNA2006100754447A CN200610075444A CN1847457A CN 1847457 A CN1847457 A CN 1847457A CN A2006100754447 A CNA2006100754447 A CN A2006100754447A CN 200610075444 A CN200610075444 A CN 200610075444A CN 1847457 A CN1847457 A CN 1847457A
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etch
rate
etching solution
precious metal
acid
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CN1847457B (en
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高桥秀树
黑岩健次
加藤胜
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Kanto Chemical Co Inc
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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • 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
    • C23F1/02—Local etching
    • 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
    • C23F1/30—Acidic compositions for etching other metallic material
    • 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
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • ing And Chemical Polishing (AREA)
  • Weting (AREA)
  • Electrodes Of Semiconductors (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

Abstract

The present invention provides an environmentally-friendly etching solution which prevents corrosion of a base metal, improves a yield and is excellent in safety compared to an aqueous solution comprising a cyanide or a lead compound when etching a noble metal on a semiconductor material comprising both the noble metal and the base metal. The iodine etching solution for etching the noble metal on the semiconductor material comprising both the noble metal and the base metal has an etching rate ratio for the noble metal to the base metal (etching rate of the noble metal/etching rate of the base metal) of >=0.03.

Description

Metal selective etching liquid
Technical field
The present invention relates to employed etching solution, particularly employed etching solution and engraving method in the microfabrication operation of gold or au-alloy distribution in the manufacturing of semiconductor device, liquid crystal indicator, IC-card etc.
Background technology
Because corresponding with miniaturization, the multifunction of nearest mobile phone, portable information terminal, digital camera etc., the package technique of IC, LSI is also developing towards miniaturization, densification direction.In order to improve the packing density of various parts, as multilayer wired method of joining up and down, used the flip-chip mode of the microspike shape electrode that is called as salient point (bump) to become main flow, use etching solution in the formation operation of the salient point of this mode.
As former iodine was etching solution, known to not making forming and the etching solution that contains organic solvent and tensio-active agent (for example patent documentation 1,2) that performance changes of etching solution.But do not know that but when having precious metal and base metal to coexist as in the semiconductor material, this etching solution is the etching precious metal optionally.
In addition, also known have not cause coarse and gold or au-alloy film that will form any thickness in the above optionally carry out etching method (for example patent documentation 3), the method (for example patent documentation 4) of only optionally dissolving precious metal and reclaiming from the metallic substance that the coexistence of precious metal and base metal is arranged to substrate surfaces such as semiconductor wafers.But the inhibition base metal corrosive effect of these methods and the etch effect of precious metal are all insufficient, and, also have the problem that security and environment aspect are short of.
Patent documentation 1: the spy opens the 2004-21142 communique
Patent documentation 2: the spy opens the 2003-109949 communique
Patent documentation 3: the spy opens clear 58-16074 communique
Patent documentation 4: the spy opens flat 6-340932 communique
Summary of the invention
Base metal generation corrosive problem when the objective of the invention is to be suppressed at etching and have the precious metal on the semiconductor material of precious metal and base metal coexistence, and raising yield rate, in addition, the present invention also aims to provide a kind of and compare excellent in safety and the etching solution few environmental influence with the aqueous solution that with prussiate and lead compound is composition.
The present inventor is in view of above-mentioned truth, carried out research with keen determination repeatedly, confirmed when the semiconductor material that makes the coexistence of precious metal and base metal impregnated in the etching solution of iodine system, with make base metal simple substance dipping and the time compare, by the cell reaction that the potential difference by the standard potential of precious metal and base metal causes, base metal is corroded.Further study, found that the ratio (etch-rate of the etch-rate/base metal of precious metal) and actual substrate (real substrate that the semiconductor material that the coexistence of precious metal and base metal is arranged are carried out the etch-rate of precious metal that etched iodine is etching solution and base metal) on the corrosion of base metal relevant, by such value is set at specific value, can address the above problem in the lump, thereby finish the present invention.
Promptly, the present invention relates to above-mentioned etching solution, it is that the iodine of etching precious metal is etching solution from the semiconductor material that the coexistence of precious metal and base metal is arranged, the ratio (etch-rate of the etch-rate/base metal of precious metal) of the precious metal of this etching solution and the etch-rate of base metal be 0.03 or more than.
The invention still further relates to above-mentioned etching solution, it contains a kind, two or more contain the organic compound of nitrogen-atoms or dissociated ion from the ammonium salt of mineral acid (still, except haloid acid).
The invention still further relates to above-mentioned etching solution, the organic compound that wherein contains nitrogen-atoms also further contains the two keys of carbon oxygen.
The invention still further relates to above-mentioned etching solution, the organic compound that wherein contains two keys of carbon oxygen and nitrogen-atoms is amide compound, amine compound or imide compound.
The invention still further relates to above-mentioned etching solution, wherein amide compound is N-N-methyl-2-2-pyrrolidone N-, 2-Pyrrolidone, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolone or N-methylformamide.
The invention still further relates to above-mentioned etching solution, wherein mineral acid is sulfuric acid, sulfurous acid, persulfuric acid or phosphoric acid.
The invention still further relates to above-mentioned etching solution, wherein precious metal is a gold.
The invention still further relates to aforesaid method, it is the method for etching precious metal from the semiconductor material that the coexistence of precious metal and base metal is arranged, it is characterized in that, by the ratio (etch-rate of the etch-rate/base metal of precious metal) that uses precious metal and the etch-rate of base metal be 0.03 or above iodine be etching solution, precious metal is optionally carried out etching.
When having confirmed that by the present invention precious metal and base metal coexist in solution, owing to cell reaction dissolves base metal, but the present invention introduces the benchmark value that is called precious metal and the ratio of the etch-rate of base metal again, the corrosion of finding the base metal on this value and the actual substrate is relevant, by be 0.03 or more than, can suppress the corrosion of base metal, and improve the etching power of precious metal.
Etching solution of the present invention is when etching precious metal from the semiconductor material that the coexistence of precious metal and base metal is arranged, precious metal by using this etching solution and the ratio of the etch-rate of base metal are 0.03 or above etching solution, even when the bigger metal of the such corrosion potential difference of gold and aluminium contacts, also can suppress the crevice corrosion of base metal, but also can improve the etching power of precious metal.
In addition, by add a kind, two or more contain nitrogen-atoms, particularly contain the organic compound of two keys of carbon oxygen and nitrogen-atoms or from mineral acid (still, except haloid acid) ammonium salt in dissociated ion, can further suppress the corrosion of base metal, and improve the etching power of precious metal.And, when the organic compound that contains two keys of carbon oxygen and nitrogen-atoms is amide compound, amine compound or imide compound, can further suppresses the corrosion of base metal, and improve the etching power of precious metal.
Particularly amide compound is N-N-methyl-2-2-pyrrolidone N-, 2-Pyrrolidone, N, N-N,N-DIMETHYLACETAMIDE, 1, when 3-dimethyl-2-imidazolone or N-methylformamide, can further suppress the corrosion of base metal, and the etching power of raising precious metal, in addition, because hypotoxicity, low foul smell and high flash point, therefore low to the influence of human body, even also can be used as non-hazardous material, handles heavy addition.
In addition, when mineral acid is sulfuric acid, sulfurous acid, persulfuric acid or phosphoric acid, can further suppress the corrosion of base metal, and improve the etching power of precious metal.In addition owing to do not use organism, aspect environment and secure context be useful.
In addition, when precious metal was gold, optionally etch gold was preferred for semiconductor substrate etc.
And, engraving method of the present invention by the ratio (etch-rate of the etch-rate/base metal of precious metal) that uses precious metal and the etch-rate of base metal be 0.03 or above iodine be etching solution, can not corrode base metal and easily precious metal is optionally carried out etching.
Description of drawings
Etch-rate when Fig. 1 is illustrated in gold when using NMP-aluminium contact, proximal line be the etch-rate of gold and aluminium, columnar shaft is the ratio of the etch-rate of golden and aluminium.
Etch-rate when Fig. 2 is illustrated in gold when using ammonium sulfate-aluminium contact, proximal line be the etch-rate of gold and aluminium, columnar shaft is the ratio of the etch-rate of golden and aluminium.
Etch-rate when Fig. 3 is illustrated in gold when using the 1-propyl alcohol-aluminium contact, proximal line be the etch-rate of gold and aluminium, columnar shaft is the ratio of the etch-rate of golden and aluminium.
Embodiment
As the precious metal among the present invention, can list for example platinum family such as gold and silver and platinum and palladium.On the other hand, as base metal, can list above-mentioned precious metals such as basic metal, alkaline-earth metal, aluminium, zinc, copper, nickel or lead metal in addition.Wherein, the etching problem when suppressing with the precious metal coexistence also improves the aspect of yield rate, preferably uses aluminium.
As the semiconductor material among the present invention, can list semiconductor substrate, silicon chip, transparent conductivity electrode etc.Wherein, preferably use semiconductor substrate.
Iodine of the present invention is that etching solution can be the known etching solution that contains iodine, iodide and water, as long as realize effect of the present invention, also can contain other composition arbitrarily.
Among the present invention the semiconductor material to the coexistence of precious metal and base metal is arranged of employed etching solution carry out the ratio (etch-rate of the etch-rate/base metal of precious metal) of etched precious metal and the etch-rate of base metal be 0.03 or more than.In order more effectively to suppress the corrosion of base metal, be preferably 0.05 or more than, be preferably especially 0.08 or more than.
Here so-called precious metal is the semiconductor material that has precious metal and base metal to coexist of the same area to be immersed in carry out etching in the etching solution with the ratio of the etch-rate of base metal, calculate etch-rate from weighting method, thereby calculate the etch-rate of the etch-rate/base metal of precious metal.
Employed etching solution specifically further adds in the etching solution of iodine system and makes the ratio of precious metal and the etch-rate of base metal reach 0.03 or above compound among the present invention, as concrete employed compound, can list the organic compound that contains nitrogen-atoms, (still from mineral acid, except haloid acid) ammonium salt in dissociated ion, 1, carbonatomss such as 4-butyleneglycol are 3 or carbonic ether such as above diol compound, acetate, tetrahydrofuran (THF), NSC 11801 etc.
With respect to etching solution, preferably use such compound of 1～85 capacity %, more preferably 10～60 capacity % are preferably 20～50 capacity % especially.
Particularly preferably be the organic compound that contains nitrogen-atoms or from mineral acid (dissociated ion in) the ammonium salt still, except haloid acid, and, in containing the organic compound of nitrogen-atoms, preferably have the compound of the two keys of carbon oxygen.
The employed organic compound that contains nitrogen-atoms can list amide compound, amine compound or imide compound etc. particularly among the present invention.
As employed amide compound among the present invention, can list the N-methylformamide, N, dinethylformamide, N, the N-diethylformamide, the N-methylacetamide, N, the N-N,N-DIMETHYLACETAMIDE, the N-methyl propanamide, N-N-methyl-2-2-pyrrolidone N-(NMP), 2-Pyrrolidone, 1,3-dimethyl-2-imidazolone, acrylamide, hexanediamide, ethanamide, 2-ethanamide vinylformic acid, 4-ethanamide M-nitro benzoic acid, 2-ethanamide M-nitro benzoic acid methyl esters, the ethanamide ethyl acetate, 4-ethanamide phenol, 2-ethanamide fluorenes, 6-ethanamide caproic acid, to the ethanamide phenyl aldehyde, 3-ethanamide diethyl malonate, 4-ethanamide butyric acid, thionamic acid, Ammonium sulfamate, amidol, 3-amino-benzene acid amides, sulfanilic amide, anthranilamide, Isonicotinamide, the N-N-isopropylacrylamide, N-sec.-propyl-1-piperazine ethanamide, urea acid amides lyase, the 2-Lucamide, along the docosene acid amides, oleylamide, the 2-chlor(o)acetamide, glycyl amide hydrochloride, succinic diamide, succinic diamide, salicylic amide, the 2-malonamide nitrile, the 2-cyano-thioacetamide, diethylamide, diacetone acrylamide, diisopropyl formamide, N, N-di-isopropyl isobutyramide, N, N-diethyl aceto-acetamide, N, the N-diethyl acetamide, N, N-diethyl 12 carboxamides, N, nicamide, the dicyano diamide, N, the N-dibutyl formamide, N, the N-Valpromide, N, N-dimethyl propylene acid amides, N, N-dimethyl benzene acid amides, stearylamide, sulfanilic amide, Sulpiride, thionamic acid, dansyl amide, thioacetamide, Thioisonicotinamide, thiobenzamide, 2-oil of mirbane acid amides, 3-oil of mirbane acid amides, 2-oil of mirbane acid amides, the 2-nitrobenzene sulfonamide, the 3-nitrobenzene sulfonamide, the 4-nitrobenzene sulfonamide, the pyrroline acid amides, pyrazinoic acid amide, the 2-phenylbutanamides, phenylbenzamide, phenoxy-acetamide, phthalic diamide, the phthalic acid diamide, fumaramide, N-butyl ethanamide, the N-butyramide, propionic acid amide, propionic acid amide, hexanamide, benzamide, benzsulfamide, methane amide, Malonamide, the propanedioic acid diamide, Toluidrin, N-methylbenzene acid amides, N-methyl-maleic acid monoamide, iodo-acid amide.
As amine compound, can list urea, glycine, imino-acetic acid, N-acetyl ethanolamine, acetyl diphenylamine, allylamine, the hydrochloric acid allylamine, the allyl group hexahydroaniline, allylamine, isobutylamine, Yi Bingchunan, Isopropylamine, thanomin, diethanolamine hydrochloride, ethylamine hydrochloride, the N-ehtylethanolamine, the N-ethylethylenediamine, the N-ethyl diisopropylamine, the N-ethyldiethanolamine, N-ethyl dicyclohexyl amine, N-ethyl-N-butylamine, 2 ethyl hexylamine, the N-ethyl benzyl amine, the N-ethyl dimethylamine, ethylenediamine sulfate, EDTA, EDTA tripotassium trihydrate, EDTA trisodium dihydrate, quadrol, hydrochloric acid ethoxy amine, diallylamine, diisobutylamine, diisopropanolamine (DIPA), Diisopropylamine, diethanolamine, diethanolamine hydrochloride, diethylamine, N-Ethylethanamine hydrochloride, diethylenetriamine, dicyclohexyl amine, pentanoic, Diphenylammonium chloride, Dimethylammonium chloride, N, the N-dimethyl allylamine, the amber amino acid, stearylamide, the hydrochloric acid stearylamide, thionamic acid, vitamin, sulfuric acid VitB1, tri-isopropanolamine, tri-isoamylamine, triethylenediamine, triphenylamine, tribenzylamine, the trimethylene diamines, Monoethanolamine MEA BASF, the hydrochloric acid Monoethanolamine MEA BASF.
As imide compound; can list succinimide; N-Hydroxysuccinimide; N-iodine succinimide; N-acryloxy succinimide; N-ethanoyl phthalic imidine; the 3-aminophthalimide; the 4-aminophthalimide; the N-aminophthalimide; imidazolidine urea (imidurea); the N-ethyl phthalimide; the N-ethyl maleimide; N-ethoxycarbonyl phthalic imidine; carbodiimide; N-chloro-succinimide; the epoxy imide; 2; 6-Phygon chlorine imide; 3; 3-dimethyl-penten imide; 1,8-naphthalimide; 3-nitro phthalic imidine; 4-nitro phthalic imidine; the N-hydroxyphthalimide; potassium phthalimide; maleimide; N methyl succinimide; chains such as iodine succinimide; the cyclic compound.Wherein, the compound that preferably contains the two keys of carbon oxygen.Preferably can suppress the burn into of base metal further especially and improve the amide compound molten of the etching power of precious metal, preferred especially NMP, 2-Pyrrolidone, N-methylformamide with water.
The concentration that contains the organic compound of nitrogen-atoms like this is preferably 1～85 capacity % with respect to etching solution, and more preferably 10～60 capacity % most preferably are 20～50 capacity %.As scope in, then can suppress the corrosion of base metal, and etching precious metal optionally.And pyrophoric danger is also low, at economic aspect very big advantage is arranged.
In addition, the addition of known NMP is when water surpasses 15 weight % less than 85 weight %, and flash-point disappears, and, almost there be not foul smell and toxicity to wait the convenience aspect security and the environment higher less yet.
On the other hand, the ammonium salt of employed mineral acid is the ammonium salt of the mineral acids such as sulfuric acid, sulfurous acid, phosphoric acid, thiosulfuric acid, thiocyanic acid, persulfuric acid, nitric acid or Hypophosporous Acid, 50 except haloid acid among the present invention.Can list ammonium thiocyanate particularly, ammonium sulfate, ammonium sulphite, primary ammonium phosphate, Secondary ammonium phosphate, triammonium phosphate, ammonium persulphate, ammonium nitrate, ammonium hypophosphite, aluminium ammonium sulfate 12 hydrates, chromium ammonium suplhate (III) 12 hydrates, cobaltous ammonium sulfate (II) hexahydrate, ammonium sulfate iron (II) hexahydrate, Tetraamminecopper Sulfate (II) hexahydrate, nickel ammonium sulfate (II) hexahydrate, ammonium sulfate magnesium hexahydrate, ammonium sulfate manganese (II) hexahydrate, chromium sulphate (III) ammonium 12 hydrates, rose vitriol (II) ammonium hexahydrate, sulfuric acid four ammonium cerium (IV) tetrahydrates, sulfuric acid four ammonium cerium (IV) dihydrates, monoammonium sulfate, monoammonium sulfate, sodium ammonium biphosphate, Secondary ammonium phosphate etc.Wherein, preferably can suppress the burn into of base metal and improve ammonium sulfate, primary ammonium phosphate, the Secondary ammonium phosphate of the etching power of precious metal especially.
The concentration of the ammonium salt of mineral acid is preferably 1～85 weight % with respect to etching solution like this, and more preferably 10～60 weight % most preferably are 30～50 weight %.As scope in, etching precious metal optionally then, and suppress the corrosion of base metal.And pyrophoric danger is also low, at economic aspect very big advantage is arranged.
In addition, dissociated ion is a dissociated ion when instigating the ammonium salt of mineral acid to be aqueous solution state from the ammonium salt of mineral acid, can list the negatively charged ion and the positively charged ion of above-claimed cpd.Be in particular ammonium ion, sulfate ion, sulfurous acid ion, biphosphate ion, phosphoric acid hydrogen ion, phosphate ion etc.
In etching solution of the present invention, use and contain the organic compound of nitrogen-atoms or from the ammonium salt of mineral acid during dissociated ion, can in etching solution, contain a kind of any class, two or more, also the combination of two classes can be contained two or more in etching solution.
This compound comprises liquid and any form of solid at normal temperatures, from the viewpoint of convenience, and preferably molten liquid form with water.
Etching solution of the present invention can known iodine be the ratio that adds the precious metal make etching solution and the etch-rate of base metal in the etching solution be 0.03 or above compound make, perhaps iodine, iodide and this compound are made in water.In addition, needn't prepare etching solution of the present invention in advance, be etching solution and this compound by using iodine when the etching, also can the etching precious metal.
As engraving method of the present invention,, can use known any method as long as use etching solution of the present invention.Impregnation method and spray regime are usually arranged, and any mode can be corresponding, but the viewpoint that changes from the composition of etching solution, preferred impregnation method.As concrete method, can be static or shake the etching of carrying out precious metal by in the groove of etching solution, making semiconductor substrate.Etching period be 1～60 minute just very abundant, can be to carry out under 20～50 ℃ in etch temperature.
Embodiment
Below, explain the present invention according to embodiment, but the present invention is not limited to these embodiment.Can in the scope that does not change its main idea, implement by appropriate change.
(reference example 1)
Etch-rate when expression gold and aluminium not impregnated in the etching solution under the state of contact.
The preparation potassiumiodide is that 30g/l, iodine are that the aqueous solution of 6g/l is as golden etching solution.
Then, implementing thickness in the Ni of 2 * 2cm test piece is the electrogilding of 3 μ m, and to be immersed in the liquid temperature be in 30 ℃ the above-mentioned etching solution 1 minute, carries out etching.Use the test piece of identical size, similarly aluminium is also carried out etching, calculate the etch-rate of gold and aluminium by weighting method with gold.The results are shown in table 1.
Etch-rate on table 1 metal simple-substance
The etch-rate of Au (nm/min.) The etch-rate of Al (nm/min.)
Reference example 1 117 0
As shown in Table 1, even aluminium simple substance is immersed in the golden etching solution, aluminium is not corroded fully yet.In contrast to this, by the comparative example 1 of table 2 as can be known, when impregnated in the golden etching solution under making gold and aluminium state of contact, golden etch-rate is reduced to about 1/60, and aluminium is corroded in large quantities.Can confirm thus, on the semiconductor substrate of gold and aluminium coexistence, owing to the aluminium corrosion causes the reduction of yield rate to be because the golden partial cell reaction that causes with contacting of aluminium.
(embodiment 1)
Suppose the etched test of the gold on the wafer that gold and aluminium coexists.
At potassiumiodide is that 30g/l, iodine are the N-N-methyl-2-2-pyrrolidone N-(NMP) that cooperates 20,30,40,50 capacity % in the aqueous solution of 6g/l respectively, prepares 4 kinds of etching solutions, each 200ml.
Then, implementing thickness in the Ni of 2 * 2cm test piece is the electrogilding of 3 μ m, with masking tape itself and onesize aluminium test piece is sticked together.It is in 30 ℃ the above-mentioned etching solution 1 minute that this test piece is immersed in the liquid temperature, carries out etching, calculates the etch-rate of gold and aluminium by weighting method.In addition, the high etch-selectivity to gold when using all cpds in order visually to show in etching solution is calculated the pairing gold of addition of every each compound and the ratio of the etch-rate of aluminium (etch-rate of the etch-rate/aluminium of gold).Certainly, wish that at this moment the etch-rate of gold is constant, and have only the etch-rate of aluminium to reduce.The results are shown in table 2 and Fig. 1.
As table 2 and shown in Figure 1, when not adding NMP, gold is 0.01 with the ratio of the etch-rate of aluminium, and when adding 50 capacity %, increases to 0.34.When using NMP like this, can not reduce the dissolving power of gold and suppress the corrosion of aluminium significantly, and can change the etching selectivity of gold and aluminium.
(embodiment 2)
Use ammonium sulfate to replace the NMP of embodiment 1, preparation has cooperated 4 kinds of aqueous solution of the ammonium sulfate of 10,20,30,40 weight %, in addition, adopts the method identical with embodiment 1 to test.The results are shown in table 2 and Fig. 2.
As table 2 and shown in Figure 2, when adding ammonium sulfate, the etch-rate of gold and aluminium is opposite, and gold increases and the aluminium minimizing, therefore, and the ratio of the etch-rate the when ratio of the etch-rate when adding 40 weight % can be higher than the NMP that adds 50 capacity %.Can not reduce the solvency power of gold thus and suppress the corrosion of aluminium significantly.
(comparative example 1)
The golden etching solution 200ml of preparation reference example 1 adopts the method identical with embodiment 1 to test.The results are shown in table 2.
As shown in table 2, aluminium is etched in large quantities as can be known.
(comparative example 2)
Preparation has cooperated 4 kinds of aqueous solution of the 1-propyl alcohol of 20,30,40,50 capacity % in the golden etching solution of reference example 1, adopt the method identical with embodiment 1 to test.The results are shown in table 2 and Fig. 3.
As table 2 and shown in Figure 3, when the etch-rate of gold reduced, gold also reduced with the ratio of the etch-rate of aluminium.This be because the 1-propyl alcohol that is used for additive can not to relax the corrosion potential of gold and aluminium poor.
Etch-rate during table 2 Au-Al contact
Addition (vol%) The etch-rate of Au (nm/min.) The etch-rate of Al (nm/min.) The ratio (Au/Al) of etch-rate
Comparative example 1 Do not have - 2 205 0.01
2 The 1-propyl alcohol 20 1 117 0.01
30 1 67 0.01
40 1 67 0.01
50 1 67 0.01
Embodiment 1 N-methyl-2-pyrrolidone 20 4 79 0.05
30 6 77 0.08
40 10 54 0.19
50 8 24 0.34
2 Ammonium sulfate 10wt％ 9 164 0.05
20wt％ 26 71 0.37
30wt％ 52 10 5.20
40wt％ 46 7 6.57
(embodiment 3)
As known from Table 2, according to the difference of compound addition, the selection of gold and aluminium is than also changing.Below, the relation between the corrosion of the aluminium on the substrate of the ratio of etch-rate like this and inhibition reality is tested.
(making of actual substrate)
Making the size of per 1 IC (containing electric capacity and resistance) on the silicon chip is 3.2 * 8mm, makes the aluminium exposed division of 10 100 * 100 μ m in IC, configuration resistance and electric capacity.Form passive film in all the other all parts except above-mentioned aluminium exposed division then.The distribution of aluminium or pad (pad) portion links to each other with resistance or electric capacity, therefore, in etching solution, owing to the current potential of resistance and electric capacity and the difference of aluminium current potential cause cell reaction, thus the aluminium of corrosion exposed division.
(test method)
Preparation is that 30g/l, iodine are 4 kinds of aqueous solution that cooperate the NMP of 10,20,30,40 capacity % in the aqueous solution of 6g/l at potassiumiodide.
Then, with the substrate of reality be the test piece of 1.5 * 1.5cm to be immersed in the liquid temperature be in above-mentioned 4 kinds of etching solutions of 30 ℃ 30 minutes, measure the number of corrosion place of aluminium exposed division.
The results are shown in table 3.8 corrosion in 10 aluminium exposed divisions of comparative example 3, and adding in the composition of NMP, by add 30 capacity % or more than, can make aluminium corrosion portion is zero.Can think that thus in order to eliminate the corrosion of aluminium, not only the etch-rate with aluminium is relevant, also the etch-rate with gold is relevant.As shown in Table 3, the ratio of gold and the etch-rate of aluminium be 0.03 or more than, then given play to and suppressed aluminium corrosive effect, be 0.08 or more than, then almost can stop the corrosion of aluminium.
(comparative example 3)
With potassiumiodide be 30g/l, iodine be the aqueous solution of 6g/l as golden etching solution, measure similarly to Example 3.The results are shown in table 3.
The affirmation (30 ℃ flooded 30 minutes) of Al corrosive effect on the substrate of table 3 inhibition reality
Addition (capacity %) The number of corrosion place of Al exposed division The ratio of Au and the etch-rate of Al
Comparative example 3 - 8 0.01
Embodiment 3 (NMP) 10 3 0.03
20 1 0.05
30 0 0.08
40 0 0.19
(embodiment 4)
By embodiment 3 as can be known, the gold and the selection of aluminium than be 0.03 or above additive can suppress the corrosion of aluminium.To be worth as benchmark value (benchmark that suppresses the aluminium corrosive effect), have the exploration of the compound that suppresses the aluminium corrosive effect.
Except with the NMP of embodiment 1 and addition is as shown in table 4 replace, other adopts the method identical with embodiment 1 to test.The results are shown in table 4.As shown in Table 4, the ratio of the corrosion of the aluminium etch-rate that almost can stop be 0.08 or above additive be to contain the two keys of carbon oxygen and the organic compound of nitrogen-atoms or the ammonium salt of mineral acid.If use these compounds, then can in the dissolving power that improves gold, suppress the corrosion of aluminium.
(comparative example 4)
Except with the NMP of embodiment 1 and addition is as shown in table 4 replace, other adopts the method identical with embodiment 1 to test.The results are shown in table 4.
Etch-rate during table 4 Au-Al contact
Addition (vol%) The etch-rate of Au (nm/min.) The etch-rate of Al (nm/min.) The ratio (Au/Al) of etch-rate
Embodiment 4 1, the 4-butyleneglycol 40 2 60 0.03
Acetate 40 3 101 0.03
Tetrahydrofuran (THF) 40 2 71 0.03
Vinyl carbonate 40 6 124 0.05
2-Pyrrolidone 40 8 47 0.17
1,3-dimethyl-2-imidazolone 40 6 47 0.12
N,N-dimethylacetamide 40 9 67 0.13
The N-methylformamide 40 14 84 0.17
Ammonium sulfate 400g/L 46 7 6.79
Comparative example 4 Ethanol 40 2 111 0.02
Ethylene glycol 40 2 94 0.02
Lactic acid 40 0 81 0
(embodiment 5)
As shown in Table 4, the ratio that ammonium salt demonstrates etch-rate is higher than other value, and it is higher that it suppresses aluminium corrosive effect.Then, use each ammonium salt to confirm the inhibition corrosive effect of different functional groups.
Except the ammonium sulfate with embodiment 4 400 (g/l) replaced with the compound of 2 shown in the table 5 (mol/l), other adopted the method identical with embodiment 4 to test.The results are shown in table 5.As shown in Table 5, almost can stop the ammonium salt of aluminium corrosive ammonium salt for the mineral acid of sulfuric acid based except that the haloid acid class and phosphoric acid class, organic acid ammonium salts such as carboxylic-acid then do not suppress corrosive effect.
(comparative example 5)
Except as shown in table 5 replacement of 400 (g/l) ammonium sulfate with embodiment 4, other adopts the method identical with embodiment 4 to test.The results are shown in table 5.
Etch-rate during table 5 Au-Al contact
The etch-rate of Au (nm/min.) The etch-rate of Al (nm/min.) The ratio (Au/Al) of etch-rate
Embodiment 5 Ammonium sulphite 43 5 0.91
Primary ammonium phosphate 56 0 -
Secondary ammonium phosphate 8 0 -
Triammonium phosphate 2 10 0.19
Comparative example 5 Ammonium chloride 3 228 0.01
Ammonium iodide 6 268 0.02
Ammonium formiate With Iod R
Ammonium acetate 32 144 0.02
Ammonium citrate 9 The white precipitate adheres to -
Succinic acid ammonium salt The black precipitate adheres to The white precipitate adheres to -
Ammonium tartrate 2 195 0.01
Ammonium benzoate 78 Yellow precipitate adheres to -
(embodiment 6)
In above-mentioned test, measured the surface-area of gold and aluminium separately etch-rate when identical, but the aluminium surface nearly all is passivated film and is protecting on the substrate of reality, so compare with the surface-area of gold, the surface-area of aluminium is very little.In this test, be determined at the surface-area of fixing gold and when the surface-area of aluminium is dwindled, to the influence of the etch-rate on each substrate.
Except the golden etching solution of the NMP that contains 50 capacity % that uses embodiment 1 comes the size of the aluminium test piece of alternative embodiment 1, carry out outside 5 minutes be etched with, other adopts the method identical with embodiment 1 to test.The results are shown in table 6.
The result of table 6 is: even under the state of the area of fixing gold the area of aluminium is dwindled, gold does not almost change with the ratio of the etch-rate of aluminium yet.Hence one can see that, compares with no interpolation system, even on the substrate that expose area less reality of aluminium with respect to gold, the inhibition corrosive effect of NMP also is effective.
(embodiment 7)
Except the NMP with 50 capacity % replaced with the ammonium sulfate of 400g/l, other adopted the method identical with embodiment 6 to test.The results are shown in table 6.The result of table 6 is: even under the state of the area of fixing gold the area of aluminium is dwindled, gold does not almost change with the ratio of the etch-rate of aluminium yet.Hence one can see that, compares with no interpolation system, even on the substrate that expose area less reality of aluminium with respect to gold, the inhibition corrosive effect of ammonium sulfate also is effective.
(comparative example 6)
Except the golden etching solution that in embodiment 6, will not contain NMP as experimental liquid, other adopts the method identical with embodiment 6 to test.The results are shown in table 6.
Etch-rate during table 6 Au-Al contact
The area ratio of Al: Au Etch-rate (nm/min.) The ratio (Au/Al) of etch-rate
Au Al
Embodiment 6 10∶10 2 48 0.042
5∶10 5 97 0.052
1∶10 27 415 0.065
Embodiment 7 10∶10 17 46 0.367
5∶10 26 81 0.323
1∶10 41 131 0.313
Comparative example 6 10∶10 5 226 0.020
5∶10 2 409 0.005
1∶10 26 1625 0.016
(embodiment 8)
Can confirm by the foregoing description, by being to add a kind of organic compound that contains two keys of carbon oxygen and nitrogen-atoms or mineral acid in the etching solution (still, except haloid acid) ammonium salt has the aluminium of inhibition corrosive effect at iodine.
Confirmed below adding two or more these gold and the etch-rate of aluminium and the ratio of etch-rate when having the compound that suppresses the aluminium corrosive effect.
Use N-N-methyl-2-2-pyrrolidone N-, 2-Pyrrolidone, N, N-N,N-DIMETHYLACETAMIDE, these 4 kinds conducts of N-methylformamide suppress aluminium corrosive compound, from wherein making up 2 kinds of compounds, potassiumiodide be 30g/l, iodine be in the aqueous solution of 6g/l every kind add 20 capacity % (adding up to 40 capacity %), adopt the method identical to test with embodiment 1.The results are shown in table 7.Result by table 7 can confirm, no matter which kind of is formed, the ratio of etch-rate reach all that the aluminium corrosion almost can stop 0.08 or more than, in the composition of 2 kinds of compound systems, also can suppress the corrosion of aluminium.
The etch-rate of 2 kinds of compound systems of table 7 and the ratio of etch-rate
Compound (20vol%+20vol%) The etch-rate of Au (nm/min.) The etch-rate of Al (nm/min.) The ratio (Au/Al) of etch-rate
Embodiment 8 N-N-methyl-2-2-pyrrolidone N-+2-Pyrrolidone 8 47 0.17
N-N-methyl-2-2-pyrrolidone N-+N,N-dimethylacetamide 8 47 0.17
N-N-methyl-2-2-pyrrolidone N-+N-methylformamide 7 71 0.10
N-methylformamide+N,N-dimethylacetamide 6 71 0.08

Claims (8)

1. etching solution, it is an etching solution for iodine of etching precious metal from the semiconductor material that the coexistence of precious metal and base metal is arranged, the ratio (etch-rate of the etch-rate/base metal of precious metal) of the precious metal of this etching solution and the etch-rate of base metal be 0.03 or more than.
2. etching solution as claimed in claim 1, it contains a kind, two or more contain the organic compound of nitrogen-atoms or dissociated ion from the ammonium salt of the mineral acid except haloid acid.
3. etching solution as claimed in claim 2, the organic compound that wherein contains nitrogen-atoms also further contains the two keys of carbon oxygen.
4. etching solution as claimed in claim 3, the organic compound that wherein contains two keys of carbon oxygen and nitrogen-atoms is amide compound, amine compound or imide compound.
5. etching solution as claimed in claim 4, wherein amide compound is N-N-methyl-2-2-pyrrolidone N-, 2-Pyrrolidone, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolone or N-methylformamide.
6. etching solution as claimed in claim 2, wherein mineral acid is sulfuric acid, sulfurous acid, persulfuric acid or phosphoric acid.
7. etching solution as claimed in claim 1, wherein precious metal is a gold.
8. engraving method, it is the method for etching precious metal from the semiconductor material that the coexistence of precious metal and base metal is arranged, it is characterized in that, by the ratio (etch-rate of the etch-rate/base metal of precious metal) that uses precious metal and the etch-rate of base metal be 0.03 or above iodine be etching solution, precious metal is optionally carried out etching.
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