TWI360586B - Etching solution for titanium or titanium alloy - Google Patents
Etching solution for titanium or titanium alloy Download PDFInfo
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- TWI360586B TWI360586B TW094114625A TW94114625A TWI360586B TW I360586 B TWI360586 B TW I360586B TW 094114625 A TW094114625 A TW 094114625A TW 94114625 A TW94114625 A TW 94114625A TW I360586 B TWI360586 B TW I360586B
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- titanium
- weight
- etching
- phosphonic acid
- etching solution
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- 238000005530 etching Methods 0.000 title claims description 47
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 24
- 229910052719 titanium Inorganic materials 0.000 title claims description 24
- 239000010936 titanium Substances 0.000 title claims description 24
- 229910001069 Ti alloy Inorganic materials 0.000 title claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- -1 phosphonic acid compound Chemical class 0.000 claims description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052718 tin Inorganic materials 0.000 claims description 11
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910001362 Ta alloys Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 1
- UDRRLPGVCZOTQW-UHFFFAOYSA-N bismuth lead Chemical compound [Pb].[Bi] UDRRLPGVCZOTQW-UHFFFAOYSA-N 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- LMRFGCUCLQUNCZ-UHFFFAOYSA-N hydrogen peroxide hydrofluoride Chemical compound F.OO LMRFGCUCLQUNCZ-UHFFFAOYSA-N 0.000 description 1
- JLLMDXDAVKMMEG-UHFFFAOYSA-N hydrogen peroxide phosphoric acid Chemical compound OO.OP(O)(O)=O JLLMDXDAVKMMEG-UHFFFAOYSA-N 0.000 description 1
- XAKRTGZVYPZHCO-UHFFFAOYSA-O hydroxy-methoxy-oxophosphanium Chemical group CO[P+](O)=O XAKRTGZVYPZHCO-UHFFFAOYSA-O 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
Landscapes
- 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)
- Inorganic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Description
1360586 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種可以從含有鈦或鈦合金和其等以 外金屬之蝕刻對象物，選擇性蝕刻鈦或鈦合金之蝕刻液及 蝕刻方法。在製造半導體製品、印刷電路基板等電子零件 方面，本發明的蝕刻液及蝕刻方法係有用的。 【先前技術】 通常蝕刻鈦或鈦合金的方法，已知有使用氟酸·硝酸 混合液、氟酸-過氧化氫混合液來處理的方法。前述的混 • 合液會同時蝕刻錫及錫合金以及鋁。又，亦已知有過氧化 氫-氣水-伸乙二胺四乙酸（鹽）混合液（參照專利文獻 1〜3 )、過氧化氫-磷酸鹽混合液（參照專利文獻4 )，然而該 等混合液對鈦或鈦合金的蝕刻速度不充分，而且，因爲過[Technical Field] The present invention relates to an etching solution and an etching method capable of selectively etching titanium or a titanium alloy from an object to be etched containing titanium or a titanium alloy and the like. The etching liquid and the etching method of the present invention are useful for producing electronic components such as semiconductor products and printed circuit boards. [Prior Art] A method of etching titanium or a titanium alloy is generally known, and a method of treating a mixture of a hydrofluoric acid/nitric acid and a hydrofluoric acid-hydrogen peroxide mixture is known. The aforementioned mixture will simultaneously etch tin and tin alloys as well as aluminum. Further, a hydrogen peroxide-gas-water-extension ethylenediaminetetraacetic acid (salt) mixed liquid (see Patent Documents 1 to 3) and a hydrogen peroxide-phosphate mixed liquid (see Patent Document 4) are known. The etching speed of the mixed solution to titanium or titanium alloy is not sufficient, and, because
氧化氫的分解顯著，無法得到安定的蝕刻。因此，要求開 發一種可以選擇性蝕刻鈦或欽合金之齡刻液及飽刻方法。 [專利文獻1]特開平8-13166號公報 [專利文獻2 ]特開平8 - 5 3 7 8 1號公報 [專利文獻3 ]美國專利第4 5 5 4 0 5 0號公報 [專利文獻4]特開2000-3 1 1 89 1號公報 【發明内容】 【發明所欲解決之課題】 本發明之目的係提供一種可以選擇性蝕刻鈦或鈦合金 之蝕刻液及蝕刻方法，不會蝕刻鈦或鈦以外的金屬，特別 是銅、錫、錫合金以及銘。 【解決課題之手段】 1360586 本發明者反覆專心檢討的結果，發現含有過氧化氫、 憐酸、膦酸系化合物、以及氨之水溶液，可以選擇性蝕刻 駄或駄合金’不會蝕刻銅、錫、錫合金以及鋁，而完成本 發明。 亦即，本發明係有關於以下之物。The decomposition of hydrogen peroxide is remarkable, and stable etching cannot be obtained. Therefore, it is required to develop an ageing and saturation method which can selectively etch titanium or alloy. [Patent Document 1] Japanese Patent Publication No. 4-5 5 0 0 0 JP-A-2000-3 1 1 89 1 SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide an etching solution and an etching method capable of selectively etching titanium or a titanium alloy without etching titanium or Metals other than titanium, especially copper, tin, tin alloys and Ming. [Means for Solving the Problem] 1360586 The inventors repeatedly reported on the results of the review and found that an aqueous solution containing hydrogen peroxide, a pity acid, a phosphonic acid compound, and ammonia can selectively etch the tantalum or niobium alloy 'will not etch copper or tin. The present invention has been completed with tin alloys and aluminum. That is, the present invention relates to the following.
u) —種蝕刻液，其特徵爲在有不容許被蝕刻的金屬 存在下’可以選擇性蝕刻鈦或鈦合金之蝕刻液，係由含有 10〜40重量％過氧化氫、〇 〇5〜5重量％磷酸、0.001〜0.1重 量％膦酸系化合物、以及氨之水溶液所構成。 (2)—種選擇性蝕刻鈦或鈦合金之蝕刻方法，其特徵 爲對含有不容許被蝕刻的金屬、以及鈦或鈦合金之蝕刻對 象物’使其與含有1〇~40重量％過氧化氫、0.05~5重量％ 磷酸、0.001 ~0.1重量％膦酸系化合物、以及氨之水溶液接u) an etching solution characterized in that an etching solution capable of selectively etching titanium or a titanium alloy in the presence of a metal which is not allowed to be etched is composed of 10 to 40% by weight of hydrogen peroxide, 〇〇 5 to 5 It is composed of a weight% phosphoric acid, a 0.001 to 0.1% by weight phosphonic acid compound, and an aqueous solution of ammonia. (2) An etching method for selectively etching titanium or a titanium alloy, which is characterized in that an etching object containing a metal which is not allowed to be etched, and a titanium or titanium alloy is caused to contain 1 to 40% by weight of peroxidation. Hydrogen, 0.05~5% by weight of phosphoric acid, 0.001~0.1% by weight of phosphonic acid compound, and aqueous solution of ammonia
【發明效果】 依據本發明之蝕刻液及蝕刻方法，可以選擇性蝕刻鈦 或鈦合金，不會蝕刻銅、錫、錫合金以及鋁。 【實施發明之最佳型態】 本發明之蝕刻液之過氧化氫濃度爲10〜40重量％，以 • 20〜30重量％爲佳。濃度小於10重量％時，對鈦及鈦合金 • 的蝕刻速度不充分，又，濃度大於40重量％時，有安全 性的問題而不佳。 磷酸有作爲過氧化氫之安定劑的效果、以及抑制錫.或 _合金溶解（蝕刻）的效果。磷酸在蝕刻液中的濃度爲 Q· 05〜5重量％，以0.1 ~1重量％爲佳。濃度小於〇.〇5重量 1360586 %時’作爲過氧化氫之安定劑的效果、以及抑制錫或錫合 金溶解（蝕刻）的效果不充分。濃度大於5重量％時，因爲 銅、錫及錫合金被蝕刻而不佳。[Effect of the Invention] According to the etching solution and the etching method of the present invention, titanium or a titanium alloy can be selectively etched without etching copper, tin, tin alloy, and aluminum. BEST MODE FOR CARRYING OUT THE INVENTION The etching solution of the present invention has a hydrogen peroxide concentration of 10 to 40% by weight, preferably 20 to 30% by weight. When the concentration is less than 10% by weight, the etching rate to titanium and the titanium alloy is insufficient, and when the concentration is more than 40% by weight, the safety is not preferable. Phosphoric acid has an effect as a stabilizer for hydrogen peroxide and an effect of suppressing dissolution (etching) of tin or alloy. The concentration of phosphoric acid in the etching solution is preferably 0.005 to 5% by weight, preferably 0.1 to 1% by weight. When the concentration is less than 〇.〇5 by weight of 1,360,586%, the effect as a stabilizer for hydrogen peroxide and the effect of suppressing dissolution (etching) of tin or tin alloy are insufficient. When the concentration is more than 5% by weight, copper, tin and tin alloys are poorly etched.
膦酸系化合物可以舉出的有伸乙二胺四（亞甲基隣 酸）、一伸乙二肢五（亞甲基膦酸）、三伸乙四胺六（亞甲基 膦酸）、丙二胺四（亞甲基膦酸）、四伸乙五胺七（亞甲基麟 酸）、六亞甲基四胺八（亞甲基膦酸）、雙（六亞甲基）三胺五 (亞甲基膦酸）、1-羥基亞乙基-1,1-二膦酸等。具有此等化 合物之膦酸基甲基的一部分，亦可被氫原子或甲基等其他 的基取代。此等膦酸系化合物的膦酸基亦可以是游離酸， 例如可以是鞍鹽之類的鹽。其中特佳之物爲二伸乙三胺五 (亞甲基膦酸）、丙二胺四（亞甲基膦酸）、1-羥基亞乙基-M 二膦酸。膦酸系化合物有作爲過氧化氫的安定劑之效果。 在触刻液中的濃度爲0.001~0.1重量，以〇·〇〇5〜0,02重 量％爲佳。小於〇 . 0 0 1重量％時，作爲過氧化氫的安定劑 之效果不充分’濃度大於0.1重量％時，因爲錫或錫合金 囊 被蝕刻而不佳。 ▼響 混合氨之目的係用以調整蝕刻液的ρ Η値。本發明的 蝕刻液之pH以7~9爲佳。因此’氨係使用將含有過氧化 氫、磷酸、膦酸系化合物之水溶液調整爲7~9之量。pH 値小於7時，對鈦及鈦合金的蝕刻速度不充分，pH値大 於9時，會促進過氧化氫的分解，而且，因爲銅、銘被倉虫 刻而不佳。 蝕刻液之製造，例如可以在水中添加過氧化氫、磷酸、 膦酸系化合物，在攪拌得到的水溶液中更添加氨水，將水The phosphonic acid compound may be exemplified by exoethylenediaminetetrakis (methylene ortho acid), hexamethylenediamine (methylenephosphonic acid), triamethylenediamine hexa(methylenephosphonic acid), and propylene. Diamine tetra (methylene phosphonic acid), tetradethyleneamine (methylene linonic acid), hexamethylenetetramine VIII (methylene phosphonic acid), bis(hexamethylene) triamine (methylene phosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, and the like. A part of the phosphonic acid methyl group having such a compound may be substituted with a hydrogen atom or another group such as a methyl group. The phosphonic acid group of these phosphonic acid compounds may also be a free acid, and may be, for example, a salt such as a saddle salt. Among them, particularly preferred are diethylenetriamine penta (methylene phosphonic acid), propylene diamine tetra (methylene phosphonic acid), and 1-hydroxyethylidene-M diphosphonic acid. The phosphonic acid compound has an effect as a stabilizer for hydrogen peroxide. The concentration in the etchant is 0.001 to 0.1% by weight, preferably 5% by weight of 〇·〇〇5 to 0,02. When the concentration is less than 0.1% by weight, the effect as a stabilizer for hydrogen peroxide is insufficient. When the concentration is more than 0.1% by weight, it is not preferable because the tin or tin alloy capsule is etched. ▼ 响 The purpose of mixing ammonia is to adjust the ρ Η値 of the etchant. The pH of the etching solution of the present invention is preferably from 7 to 9. Therefore, the ammonia solution is adjusted to an amount of 7 to 9 in an aqueous solution containing hydrogen peroxide, phosphoric acid or a phosphonic acid compound. When the pH 値 is less than 7, the etching rate for titanium and the titanium alloy is insufficient, and when the pH 値 is larger than 9, the decomposition of hydrogen peroxide is promoted, and since copper and the inscription are inferior. For the production of an etching solution, for example, hydrogen peroxide, phosphoric acid, or a phosphonic acid-based compound may be added to water, and ammonia water may be further added to the aqueous solution obtained by stirring.
1360586 溶液的pH値調整至7-9而製造得到。 本發明之蝕刻方法，可以使蝕刻對象物與蝕刻 來進行。接觸方法沒有特別限制，可以藉由浸漬處 霧處理等來進行。處理溫度以30~60°C爲佳。處理 高可以對鈦及鈦合金的蝕刻速度，但是大於6 0 °C 爲會促進過氧化氫的分解而不佳。又，蝕刻處理時 以配合蝕刻對象物的表面狀態、形狀來選擇最適 間，實用上以1 ~ 1 0分鐘爲佳。 【實施方式】 [實施例] 藉由以下實施例及比較例來具體地說明本發明 本發明並不限定於以下的實施例。 實施例1 在含有20重量％過氧化氫、0.3重量％磷酸、 量％二伸乙三胺五（亞甲基膦酸）、以及氨之調整馬 的水溶液（蝕刻液）中，於40°C浸漬下述各基板1分 (1)在矽晶圓（晶圓直徑：5吋）上使用濺鑛法形 2000A鈦膜之基板。 (2)在矽晶圓（晶圓直徑：5吋）上使用濺鍍法形 2000A銅膜之基板。 (3)在矽晶圓（晶圓直徑：5吋）上使用濺鍍法形 2000A鋁膜之基板。 (4)在SUS304材上形成厚度ΙΟΟΟΟΑ錫-鉛（6: 膜之基板（100mmxl0〇mmx〇.5mm)。 各種金屬膜的溶解速度如表1所示。 液接觸 理、噴 溫度越 時，因 間，可 當的時 ，但是 0.01 重 PH9.0 鐘。 成厚度 成厚度 成厚度 4)電鍍 1360586 比較例6 除了使用氫氧化四甲基銨代替氨以外’和實施例1同 樣地進行。結果如表1所示。 實施例41360586 The pH of the solution was adjusted to 7-9 and manufactured. The etching method of the present invention can be performed by etching an object and etching. The contact method is not particularly limited and may be carried out by a dipping treatment or the like. The treatment temperature is preferably 30 to 60 ° C. The high etching rate for titanium and titanium alloys, but greater than 60 °C, may contribute to the decomposition of hydrogen peroxide. Further, in the etching process, the optimum state is selected in accordance with the surface state and shape of the object to be etched, and it is preferably 1 to 10 minutes practically. [Embodiment] [Examples] The present invention will be specifically described by the following examples and comparative examples. The present invention is not limited to the following examples. Example 1 In an aqueous solution (etching solution) containing 20% by weight of hydrogen peroxide, 0.3% by weight of phosphoric acid, 3% by weight of diethylenetriamine penta (methylene phosphonic acid), and ammonia, at 40 ° C One board of each of the following substrates was immersed (1) A substrate of a 2000A titanium film was sputtered on a tantalum wafer (wafer diameter: 5 Å). (2) A substrate of a 2000A copper film was sputter-coated on a tantalum wafer (wafer diameter: 5 Å). (3) A substrate of a 2000 A aluminum film was sputtered on a tantalum wafer (wafer diameter: 5 Å). (4) A thickness of bismuth-lead (6: film substrate (100 mm x 10 〇 mm x 〇. 5 mm) was formed on the SUS304 material. The dissolution rates of various metal films are shown in Table 1. The liquid contact temperature and the temperature of the spray were caused by In the meantime, it can be used in the same manner as in Example 1 except that the thickness is reduced to a thickness of 4 Å. 4) Electroplating 1360586 Comparative Example 6 The same procedure as in Example 1 was carried out except that tetramethylammonium hydroxide was used instead of ammonia. The results are shown in Table 1. Example 4
在含有20重量％過氧化氫、〇·2重量％磷酸、〇·〇1重 量％二伸乙三胺五（亞甲基膦酸）、以及氨之調整爲ΡΗ 8·0 的蝕刻液中，溶解金屬鈦100毫克/升’使液體溫度保持40 °c放置8小時。放置前和放置後的過氧化氫的分解率如表 2所示。 分解率（％ )=(放置前過氧化氫濃度—放置後過氧化氫 濃度)X丨〇〇/放置前過氧化氫濃度 比較例7 除了使用含有2〇重量％過氧化氫、〇.1重量％伸乙二 月安四乙酸四鈉、以及氯之調整爲pH 8.0的水溶液（鈾刻液.) 以外，和實施例4同樣地進行。結果如表2所示。 比較例8 地缠 除了使用含有20重量％過氧化氫、以及磷酸氫二鈉 之__馬pH 8 〇的水溶液（蝕刻液）以外，和實施例4同樣 行°結果如表2所不 -10 - 1360586 [表1] • t \ -* --- 實施例1 ^— ,,m J 溶解量（A/分鐘） 鈦 銅 鋁 錫-給 1500 <10 <10 <10 實施例2 — — — 1 700 . <10 <10 <10 實施例3 — 1800 <10 <10 <10 比較例1 比較例2 ~·" — ... 1 1000 1000 2 0 00 3000 1000 1000 2000 3000 比較例3 ~ ----- 300 <10 <10 <10 比較例4 300 <10 <10 <10 比較例5 300 <10 <10 <10 比較例6 --- 200 <10 <10 <10 $D ^ 1所示，本發明之蝕刻液選擇性蝕刻鈦或鈦合 金，不會蝕刻銅、錫、錫合金以及鋁。In an etching solution containing 20% by weight of hydrogen peroxide, 〇·2% by weight of phosphoric acid, 〇·〇1% by weight of diethylenetriamine penta (methylene phosphonic acid), and ammonia adjusted to ΡΗ 8·0, Dissolve the metal titanium 100 mg / liter 'to keep the liquid temperature at 40 ° C for 8 hours. The decomposition rate of hydrogen peroxide before and after standing is shown in Table 2. Decomposition rate (%) = (concentration of hydrogen peroxide before standing - concentration of hydrogen peroxide after standing) X 丨〇〇 / concentration of hydrogen peroxide before standing Comparative Example 7 In addition to containing 2% by weight of hydrogen peroxide, 〇.1 by weight The same procedure as in Example 4 was carried out except that the sodium tetrasodium pentoxide tetraacetate and the aqueous solution of chlorine having a pH of 8.0 (uranium engraving solution) were added. The results are shown in Table 2. Comparative Example 8 The same procedure as in Example 4 was carried out except that an aqueous solution (etching solution) containing 20% by weight of hydrogen peroxide and disodium hydrogen phosphate was used, and the results were as shown in Table 2 -10 - 1360586 [Table 1] • t \ -* --- Example 1 ^— ,, m J Dissolution amount (A/min) Titanium copper aluminum tin-giving 1500 < 10 < 10 < 10 Example 2 - - 1 700 . <10 <10 <10 Embodiment 3 - 1800 < 10 < 10 < 10 Comparative Example 1 Comparative Example 2 ~·" — ... 1 1000 1000 2 0 00 3000 1000 1000 2000 3000 Comparative Example 3 ~ ----- 300 < 10 < 10 < 10 Comparative Example 4 300 < 10 < 10 < 10 Comparative Example 5 300 < 10 < 10 < 10 Comparative Example 6 --- 200 < 10 < 10 < 10 < 10 $ D ^ 1, the etching solution of the present invention selectively etches titanium or a titanium alloy without etching copper, tin, tin alloy and aluminum.
&解’可以安定地進行選擇性蝕刻鈦或鈦合金。 【圖式簡單說明】 迦 * \ w 【主要元件符號說明】 itt y\w -11 -The & solution can be selectively etched with titanium or a titanium alloy. [Simple description of the diagram] Jia * \ w [Main component symbol description] itt y\w -11 -
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| WO2009081884A1 (en) | 2007-12-21 | 2009-07-02 | Wako Pure Chemical Industries, Ltd. | Etching agent, etching method and liquid for preparing etching agent |
| JP5150401B2 (en) * | 2008-08-04 | 2013-02-20 | 株式会社アルバック | Method for manufacturing component parts of vacuum chamber, method for recycling the parts, method for manufacturing the frame, and method for recycling the frame |
| KR20120067198A (en) * | 2010-12-15 | 2012-06-25 | 제일모직주식회사 | Etching paste and method for preparing thereof, method of forming a pattern using the same |
| CN105378901B (en) | 2013-07-05 | 2020-09-15 | 富士胶片电子材料有限公司 | Etchant, etching method and etchant preparation liquid |
| US20150368557A1 (en) | 2014-06-23 | 2015-12-24 | Hyosan Lee | Metal etchant compositions and methods of fabricating a semiconductor device using the same |
| JP6545691B2 (en) * | 2014-09-19 | 2019-07-17 | 三菱電機株式会社 | Semiconductor device manufacturing method |
| JP6429079B2 (en) | 2015-02-12 | 2018-11-28 | メック株式会社 | Etching solution and etching method |
| EP3436621B1 (en) | 2016-03-29 | 2020-02-12 | Technic France | Solution and method for etching titanium based materials |
| SG11201908791SA (en) | 2017-03-31 | 2019-10-30 | Kanto Kagaku | Etchant composition for etching titanium layer or titanium-containing layer, and etching method |
| KR20200105221A (en) | 2019-02-28 | 2020-09-07 | 동우 화인켐 주식회사 | An etchant composition and an ehting method and a mehtod for fabrication metal pattern using the same |
| CN110581061B (en) * | 2019-09-25 | 2022-03-01 | 同辉电子科技股份有限公司 | Processing technology of gallium nitride MMIC power amplifier chip |
| CN114196956B (en) * | 2020-09-18 | 2024-03-12 | 珠海市丹尼尔电子科技有限公司 | Etching solution for titanium |
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