CN115433940A - Copper etching solution, preparation method and application - Google Patents
Copper etching solution, preparation method and application Download PDFInfo
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- CN115433940A CN115433940A CN202211073590.1A CN202211073590A CN115433940A CN 115433940 A CN115433940 A CN 115433940A CN 202211073590 A CN202211073590 A CN 202211073590A CN 115433940 A CN115433940 A CN 115433940A
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- 238000005530 etching Methods 0.000 title claims abstract description 99
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 64
- 239000010949 copper Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002270 dispersing agent Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 239000003112 inhibitor Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 5
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 8
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 229920000057 Mannan Polymers 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- 229960005323 phenoxyethanol Drugs 0.000 claims description 8
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012964 benzotriazole Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 4
- 229920001503 Glucan Polymers 0.000 claims description 4
- OVRNDRQMDRJTHS-UHFFFAOYSA-N N-acelyl-D-glucosamine Natural products CC(=O)NC1C(O)OC(CO)C(O)C1O OVRNDRQMDRJTHS-UHFFFAOYSA-N 0.000 claims description 4
- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 claims description 4
- MBLBDJOUHNCFQT-LXGUWJNJSA-N N-acetylglucosamine Natural products CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- XUZHLZDRCCUWEV-UHFFFAOYSA-N formaldehyde;methyl naphthalene-1-sulfonate Chemical compound O=C.C1=CC=C2C(S(=O)(=O)OC)=CC=CC2=C1 XUZHLZDRCCUWEV-UHFFFAOYSA-N 0.000 claims description 4
- 229950006780 n-acetylglucosamine Drugs 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 3
- XEGMDUOAESTQCC-UHFFFAOYSA-N 1-(naphthalen-1-ylmethyl)naphthalene;sodium Chemical compound [Na].C1=CC=C2C(CC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 XEGMDUOAESTQCC-UHFFFAOYSA-N 0.000 claims description 2
- SRDOTWUOTQTGAK-UHFFFAOYSA-N C=O.C1(=CC=CC2=CC=CC=C12)S(=O)(=O)OCC1=CC=CC=C1 Chemical compound C=O.C1(=CC=CC2=CC=CC=C12)S(=O)(=O)OCC1=CC=CC=C1 SRDOTWUOTQTGAK-UHFFFAOYSA-N 0.000 claims description 2
- 102000003886 Glycoproteins Human genes 0.000 claims description 2
- 108090000288 Glycoproteins Proteins 0.000 claims description 2
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 2
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001431 copper ion Inorganic materials 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 108010020346 Polyglutamic Acid Proteins 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 108010054442 polyalanine Proteins 0.000 description 3
- 229920002643 polyglutamic acid Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- DWHOIYXAMUMQTI-UHFFFAOYSA-L disodium;2-[(1-sulfonatonaphthalen-2-yl)methyl]naphthalene-1-sulfonate Chemical compound [Na+].[Na+].C1=CC2=CC=CC=C2C(S(=O)(=O)[O-])=C1CC1=CC=C(C=CC=C2)C2=C1S([O-])(=O)=O DWHOIYXAMUMQTI-UHFFFAOYSA-L 0.000 description 2
- LCRMGUFGEDUSOG-UHFFFAOYSA-N naphthalen-1-ylsulfonyloxymethyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(OCOS(=O)(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 LCRMGUFGEDUSOG-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 2
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- -1 alkynediol Chemical compound 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention provides a copper etching solution and a preparation method and application thereof, wherein the copper etching solution comprises phosphoric acid, strong oxidizing acid, an inhibitor, a surfactant, a dispersant and deionized water; the dispersing agent is one or a combination of a plurality of naphthalene sulfonate, lignosulfonate, sodium humate and polycarboxylate. The copper etching solution has stable performance, can effectively disperse particles, inhibits organic matters and copper ions from agglomerating, ensures that the surface of a substrate is clean and pollution-free, and can ensure that the copper etching solution has a smaller etching cone angle and a smaller CDloss variable quantity.
Description
Technical Field
The invention relates to the technical field of etching solutions, in particular to a copper etching solution, a preparation method and application thereof.
Background
Copper metal has good conductivity, so it is widely used in circuit layout, and circuit etching usually uses wet etching to etch off the metal without photoresist protection to form the circuit. At present, the copper etching solution in the market is mainly hydrogen peroxide water-based copper etching solution (such as CN 104498951B), and the instability of etching is caused because hydrogen peroxide is easy to decompose by heating; moreover, as the etching time is prolonged, the copper ion content in the liquid medicine is increased, so that the decomposition of hydrogen peroxide is promoted, the etching service life of the liquid medicine is shortened, and in addition, the decomposition and heat release of the hydrogen peroxide are easy to induce potential safety hazards. In order to ensure good etching performance of the copper etching solution, some surfactants are usually added into the copper etching solution to maintain the surface tension and wetting effect of the metal surface, but most surfactants often present aggregate forms with different shapes in organic solvents or aqueous solutions, such as micelle, bilayer film or liquid crystal forms, and the aggregate forms cause substrate contamination and instability of etching. Therefore, a non-hydrogen peroxide aqueous copper etching solution with good dispersibility and stable performance is needed.
Disclosure of Invention
In view of this, the invention provides a non-hydrogen peroxide aqueous copper etching solution with good dispersibility and stable performance, a preparation method and an application thereof.
The technical scheme of the invention is realized as follows:
in a first aspect, the invention provides a copper etching solution, which comprises phosphoric acid, strong oxidizing acid, an inhibitor, a surfactant, a dispersant and deionized water; the dispersing agent is one or a combination of a plurality of naphthalene sulfonate, lignosulfonate, sodium humate and polycarboxylate.
On the basis of the technical scheme, preferably, the etching solution comprises, by mass, 100%, 10-20% of phosphoric acid, 1-10% of a strong oxidizing acid, 0.05-1% of an inhibitor, 0.01-1% of a surfactant, 0.01-1% of a dispersant, and the balance of deionized water.
On the basis of the technical scheme, preferably, the naphthalene sulfonate is one or a combination of more of sodium methylene dinaphthalene sulfonate, a methyl naphthalene sulfonate formaldehyde condensate and a benzyl naphthalene sulfonate formaldehyde condensate; the lignosulfonate is one or more of sodium lignosulfonate, potassium lignosulfonate and calcium lignosulfonate; the polycarboxylate is one or more of TERSPERSE 2700, SD-819, GY-D1252 and SD-661 in combination.
On the basis of the technical scheme, the biological flocculant is preferably one or a combination of more of polyamino acid, glucan, mannan, glycoprotein and N-acetylglucosamine.
Based on the above technical scheme, preferably, the polyamino acid is one or more of polyglutamic acid, polyalanine and polyaspartic acid.
On the basis of the technical scheme, preferably, the etching solution comprises, by mass, 100%, 10-20% of phosphoric acid, 4-8% of strong oxidizing acid, 0.2-0.4% of inhibitor, 0.2-0.4% of surfactant, 0.3-0.4% of dispersant, 0.5-0.9% of bioflocculant, and the balance deionized water.
On the basis of the above technical solution, preferably, the strong oxidizing acid is one or a combination of sulfuric acid, hydrochloric acid, perchloric acid and nitric acid.
On the basis of the technical scheme, preferably, the inhibitor is one or a combination of more than one of 5-methyltetrazole, 5-aminotetrazole, benzotriazole and imidazole.
On the basis of the above technical scheme, preferably, the surfactant is an alcohol nonionic surfactant.
On the basis of the technical scheme, preferably, one or more of isopropanol, 2-phenoxyethanol, alkynediol and polyethylene glycol are used as the surfactant.
In a second aspect, the invention provides a method for preparing a copper etching solution, comprising the following steps: adding phosphoric acid, strong oxidizing acid and deionized water into a container, and stirring at 25 ℃ and 600-800rpm for 10-20min; then adding inhibitor, surfactant, dispersant and bioflocculant, stirring at 25 deg.C and 800-1000rpm for 10-30min.
In a third aspect, the invention provides an application of a copper etching solution, wherein the copper etching solution is used for selectively etching metal copper on a copper substrate at 32 ℃.
Compared with the prior art, the copper etching liquid and the preparation method and application thereof have the following beneficial effects:
(1) In the copper etching solution, metal copper is oxidized into copper ions under the action of phosphoric acid and strong oxidizing acid; the inhibitor is adsorbed on the surface of copper, so that the lateral erosion amount is reduced, and excessive corrosion of the etching solution is prevented; the surface active agent enables the etching solution to be fully contacted with the copper surface, so that the etching rate is improved; the inhibitor and the surfactant act synergistically to maintain the etching cone angle; the dispersing agent can effectively disperse particles, inhibit agglomeration, and ensure good etching performance and cleanness and no pollution of a substrate.
(2) In the copper etching solution, the biological flocculant can effectively adsorb excessive generated copper ions, maintain the stability of the solution, maintain a smaller etching cone angle and maintain no residue on the surface of the substrate.
(3) The etching solution of the invention can ensure that the etching cone angle is smaller, the CD loss variation is smaller, and no residue is left on the surface of the substrate.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a graph showing the comparison of the etching performance of the copper etching solution of the present invention;
FIG. 2 is a graph showing the comparison of polymer deposition in the etching solution of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments of the present invention, belong to the protection scope of the present invention.
All reagents used in the present application are commercially available reagents, and the present application is further described in detail below by way of specific examples, which are only further illustrative of the present application and should not be construed as limiting the present application.
Example 1
The copper etching solution of the embodiment comprises, by mass, 100% of phosphoric acid, 1% of sulfuric acid, 0.05% of 5-methyltetrazole, 0.01% of isopropanol, 0.01% of sodium methylenedinaphthalene sulfonate, and the balance of deionized water.
The preparation method of the copper etching solution comprises the following steps: adding phosphoric acid, sulfuric acid and deionized water into a container, and stirring at 25 ℃ and 600rpm for 10min; then adding 5-methyltetrazole, isopropanol and methylene dinaphthalene sodium sulfonate, and stirring at 25 ℃ and 800rpm for 10 min.
Example 2
The copper etching solution of the present embodiment comprises, by mass, 100% of phosphoric acid, 4% of hydrochloric acid, 0.2% of 5-aminotetrazole, 0.2% of 2-phenoxyethanol, 0.2% of sodium lignosulfonate, 0.3% of polyalanine, 0.2% of mannan, and the balance of deionized water.
The preparation method of the copper etching solution comprises the following steps: adding phosphoric acid, hydrochloric acid and deionized water into a container, and stirring at 25 deg.C and 700rpm for 15min; then adding 5-aminotetrazole, 2-phenoxyethanol, sodium lignin sulfonate, polyalanine and mannan, and stirring at 25 deg.C and 900rpm for 20min.
Example 3
The copper etching solution of the embodiment comprises, by mass, 100% of phosphoric acid, 6% of perchloric acid, 0.4% of benzotriazole, 0.3% of acetylenic diol, 0.2% of sodium methylenedinaphthalene sulfonate, 0.1% of sodium humate, 0.4% of mannan, 0.2% of glucan, and the balance of deionized water.
The preparation method of the copper etching solution comprises the following steps: adding phosphoric acid, perchloric acid and deionized water into a container, and stirring at 25 ℃ and 700rpm for 15min; then adding benzotriazole, alkynediol, sodium methylene dinaphthalene sulfonate, sodium humate, mannan and glucan, and stirring at 25 ℃ and 900rpm for 20min.
Example 4
The copper etching solution of the embodiment comprises, by mass percentage of 100%, 18% of phosphoric acid, 8% of nitric acid, 0.2% of 5-methyltetrazole, 0.2% of imidazole, 0.2% of 2-phenoxyethanol, 0.2% of propargyl alcohol, 0.3% of potassium lignosulfonate, 0.1% of TERSPERSE 2700, 0.9% of N-acetylglucosamine, and the balance being deionized water.
The preparation method of the copper etching solution comprises the following steps: adding phosphoric acid, nitric acid and deionized water into a container, and stirring at 25 ℃ and 800rpm for 20min; then 5-methyltetrazole, imidazole, 2-phenoxyethanol, propargyl alcohol, potassium lignosulfonate, TERSPERSE 2700 and N-acetylglucosamine were added and stirred at 1000rpm at 25 ℃ for 30min.
Example 5
The copper etching solution of the embodiment comprises, by mass, 100% of phosphoric acid, 10% of sulfuric acid, 0.6% of 5-methyltetrazole, 0.4% of benzotriazole, 0.4% of 2-phenoxyethanol, 0.6% of polyethylene glycol, 0.8% of a methyl naphthalene sulfonate formaldehyde condensate, 0.2% of GYD-1252,0.5% of polyglutamic acid, 0.4% of mannan, and the balance of deionized water.
The preparation method of the copper etching solution comprises the following steps: adding phosphoric acid, sulfuric acid and deionized water into a container, and stirring at 25 ℃ and 800rpm for 20min; then adding 5-methyltetrazole, benzotriazole, 2-phenoxyethanol, polyethylene glycol, methyl naphthalene sulfonate formaldehyde condensate, GYD-1252, polyglutamic acid and mannan, and stirring at 25 deg.C and 1000rpm for 30min.
Comparative example 1
The composition of the copper etching solution of comparative example 1 was prepared substantially in the same manner as in example 1 except that the composition of the copper etching solution of comparative example 1 lacked a dispersant.
Comparative example 2
The copper etching solution composition of comparative example 2 was prepared substantially in the same manner as in example 1, except that the copper etching solution composition of comparative example 1 lacks a dispersant and an inhibitor.
Comparative example 3
The copper etching solution composition of comparative example 3 was prepared substantially in the same manner as in example 1, except that the copper etching solution composition of comparative example 1 lacks a surfactant and a dispersant.
The etching methods of the examples and comparative examples were: the copper etching solution is used for selectively etching the metal copper on the copper substrate at the temperature of 32 ℃.
1. Etching performance
The copper substrate was etched at 32 ℃ using an etcher with the amount of over-etching being 100% OE, and the substrate cross-sectional view was photographed using a scanning electron microscope SEM to observe the substrate etching taper angle, CD loss and residual, and the results are shown in Table 1 and FIG. 1.
TABLE 1 etching Performance of the etching solutions of examples and comparative examples
| Etching performance | Cone angle/° c | CDLoss/μm | Residue(s) is (are) | SEM photograph |
| Example 1 | 53 | 1.18 | Is composed of | 1-A |
| Example 2 | 45 | 1.14 | Is free of | / |
| Example 3 | 40 | 1.15 | Is composed of | / |
| Example 4 | 42 | 1.12 | Is composed of | / |
| Example 5 | 44 | 1.13 | Is composed of | / |
| Comparative example 1 | 45 | 1.34 | Is provided with | 1-B |
| Comparative example 2 | 62 | 1.32 | Is provided with | 1-C |
| Comparative example 3 | 64 | 1.34 | Is provided with | 1-D |
The adsorption capacity of the inhibitor of the etching solution on different parts of the copper surface is different due to the adsorption effect of the tip, so that the adsorption capacity of the side surface is larger than that of the front surface, the etching rate of the side surface is lower than that of the front surface, the side etching amount is reduced, the cone angle is smaller, and the surfactant can reduce the interface attraction between the etching solution and the copper surface and can generate a synergistic effect with the inhibitor.
As can be seen from the data in Table 1, examples 1-5 all had good etch taper angles, no residue, and relatively stable etch performance. The dispersant is absent in comparative examples 1 to 3, so that the surface of the substrate remains, and the etching taper angle is increased in comparative examples 2 and 3 due to the absence of the inhibitor or the surfactant, and the post-plating process is affected by the excessive taper angle or the presence of the residue.
2. Whether or not the polymer precipitates
8000ppm of copper powder is added into the etching solution, the copper powder is completely dissolved at room temperature and poured into an etching machine, after the copper powder is continuously sprayed for 36 hours at 32 ℃ and 0.15Mpa, 500ml of leaching solution is taken out and filtered by a 0.8 mu m filter membrane for three times, whether precipitates appear is observed, whether attachments exist on the surface of the substrate is observed by photographing by using a Scanning Electron Microscope (SEM), and the result is shown in table 2 and figure 2.
TABLE 2 Polymer deposition results
As can be seen from table 2, in examples 2 to 5, the addition of the bio-flocculant effectively adsorbed excessive copper ions, and maintained the stability of the chemical solution, so that the chemical solution could maintain good etching performance, and the metal film layer and the etched taper angle could be clearly seen without any adhesion on the substrate surface. The lack of the dispersant and flocculant in comparative examples 1 to 3 resulted in a large amount of residue on the substrate surface, no etching angle, and poor etching performance.
3. Increased effect of copper powder on etching
2000ppm, 4000ppm and 8000ppm of copper powder are respectively dissolved in the prepared copper etching solution, a copper substrate is etched by an etching machine under the conditions of 32 ℃ and 0.15MPa, a cross section is photographed by using a Scanning Electron Microscope (SEM), the influence of the increase of the copper powder on the etching performance of the substrate is observed, and the result is shown in Table 3.
TABLE 3 influence of copper powder on etching
As shown in the data of Table 3, examples 2-5 still had good etch taper angles, more stable etch performance, and longer etch life as the copper powder content increased. In the embodiment 1, because the bio-flocculant is lacked, when the content of the copper powder is more than or equal to 8000ppm, the excessive copper ions lead the liquid medicine to be unstable, thereby reducing the etching effect and generating residues on the surface of the substrate. In comparative examples 1 to 3, the etching angle was too large, and residues were left, and the residues became serious with the increase of the copper powder content, and the increase of the copper ion content in the chemical solution also resulted in unstable etching effect, and had a certain potential safety hazard.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (10)
1. A copper etching solution is characterized in that: comprises phosphoric acid, strong oxidizing acid, inhibitor, surfactant, dispersant and deionized water; the dispersing agent is one or a combination of a plurality of naphthalene sulfonate, lignosulfonate, sodium humate and polycarboxylate.
2. The copper etching solution according to claim 1, wherein: the etching solution comprises, by mass, 100% of phosphoric acid, 1-10% of strong oxidizing acid, 0.05-1% of inhibitor, 0.01-1% of surfactant, 0.01-1% of dispersant and the balance of deionized water.
3. The copper etching solution according to claim 1, wherein: the naphthalene sulfonate is one or a combination of more of methylene dinaphthalene sodium sulfonate, a methyl naphthalene sulfonate formaldehyde condensate and a benzyl naphthalene sulfonate formaldehyde condensate; the lignosulfonate is one or more of sodium lignosulfonate, potassium lignosulfonate and calcium lignosulfonate; the polycarboxylate is one or more of TERSPERSE 2700, SD-819, GYD-1252 and SD-661 in combination.
4. The copper etching solution according to claim 1, wherein: the bioflocculant is one or more of polyamino acid, glucan, mannan, glycoprotein and N-acetyl glucosamine.
5. The copper etching solution according to claim 4, wherein: the copper etching solution comprises, by mass, 100% of phosphoric acid, 4-8% of strong oxidizing acid, 0.2-0.4% of inhibitor, 0.2-0.4% of surfactant, 0.3-0.4% of dispersant, 0.5-0.9% of bioflocculant and the balance deionized water.
6. The copper etching solution according to claim 1, wherein: the strong oxidizing acid is one or more of sulfuric acid, hydrochloric acid, perchloric acid and nitric acid.
7. The copper etching solution according to claim 1, wherein: the inhibitor is one or more of 5-methyltetrazole, 5-aminotetrazole, benzotriazole and imidazole.
8. The copper etching solution according to claim 1, wherein: the surfactant is one or more of isopropanol, 2-phenoxyethanol, alkynediol and polyethylene glycol.
9. The method for preparing a copper etching solution according to claim 4, wherein: the method comprises the following steps: adding phosphoric acid, strong oxidizing acid and deionized water into a container, and stirring at 25 ℃ and 600-800rpm for 10-20min; then adding inhibitor, surfactant, dispersant and bioflocculant, stirring at 25 deg.C and 800-1000rpm for 10-30min.
10. Use of a copper etching solution as claimed in any one of claims 1 to 8, wherein: and selectively etching the metal copper on the substrate by using a copper etching solution at the temperature of 32 ℃.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005350708A (en) * | 2004-06-09 | 2005-12-22 | Okuno Chem Ind Co Ltd | Composition for etching |
| CN101039553A (en) * | 2000-07-27 | 2007-09-19 | 阿托特希德国有限公司 | Improved adhesion of polymeric materials to metal surfaces |
| WO2010082439A1 (en) * | 2009-01-16 | 2010-07-22 | 三洋半導体製造株式会社 | Etchant composition |
| CN111334800A (en) * | 2020-04-24 | 2020-06-26 | 信丰正天伟电子科技有限公司 | Novel PCB micro-etching solution and preparation method thereof |
| CN111808612A (en) * | 2020-07-08 | 2020-10-23 | 江苏和达电子科技有限公司 | Etching solution and etching supplementary solution for copper/molybdenum (niobium)/IGZO film layer, and preparation method and application thereof |
| CN113604804A (en) * | 2021-07-07 | 2021-11-05 | 湖北兴福电子材料有限公司 | Etching solution for stabilizing line width loss and etching cone angle in panel copper plating process |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101039553A (en) * | 2000-07-27 | 2007-09-19 | 阿托特希德国有限公司 | Improved adhesion of polymeric materials to metal surfaces |
| JP2005350708A (en) * | 2004-06-09 | 2005-12-22 | Okuno Chem Ind Co Ltd | Composition for etching |
| WO2010082439A1 (en) * | 2009-01-16 | 2010-07-22 | 三洋半導体製造株式会社 | Etchant composition |
| CN111334800A (en) * | 2020-04-24 | 2020-06-26 | 信丰正天伟电子科技有限公司 | Novel PCB micro-etching solution and preparation method thereof |
| CN111808612A (en) * | 2020-07-08 | 2020-10-23 | 江苏和达电子科技有限公司 | Etching solution and etching supplementary solution for copper/molybdenum (niobium)/IGZO film layer, and preparation method and application thereof |
| CN113604804A (en) * | 2021-07-07 | 2021-11-05 | 湖北兴福电子材料有限公司 | Etching solution for stabilizing line width loss and etching cone angle in panel copper plating process |
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