JP2005320608A - Etching solution for titanium or titanium alloy - Google Patents
Etching solution for titanium or titanium alloy Download PDFInfo
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- JP2005320608A JP2005320608A JP2004141438A JP2004141438A JP2005320608A JP 2005320608 A JP2005320608 A JP 2005320608A JP 2004141438 A JP2004141438 A JP 2004141438A JP 2004141438 A JP2004141438 A JP 2004141438A JP 2005320608 A JP2005320608 A JP 2005320608A
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- 238000005530 etching Methods 0.000 title claims abstract description 51
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000010936 titanium Substances 0.000 title claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 28
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 49
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- -1 phosphonic acid compound Chemical class 0.000 claims description 8
- 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 5
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229940116254 phosphonic acid Drugs 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000003009 phosphonic acids Chemical class 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- XFLNVMPCPRLYBE-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XFLNVMPCPRLYBE-UHFFFAOYSA-J 0.000 description 2
- JCTXXFXWHMLHLS-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;hydrate Chemical compound O.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O JCTXXFXWHMLHLS-UHFFFAOYSA-N 0.000 description 1
- XWROUVVQGRRRMF-UHFFFAOYSA-N F.O[N+]([O-])=O Chemical compound F.O[N+]([O-])=O XWROUVVQGRRRMF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- SWXQKHHHCFXQJF-UHFFFAOYSA-N azane;hydrogen peroxide Chemical compound [NH4+].[O-]O SWXQKHHHCFXQJF-UHFFFAOYSA-N 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 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
- 238000007654 immersion Methods 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Classifications
-
- 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
-
- C11D2111/10—
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Description
本発明は、チタンまたはチタン合金とそれら以外の金属が存在する材料からチタンまたはチタン合金を選択的にエッチングするエッチング液およびエッチング方法に関する。本発明のエッチング方法は、半導体製品、プリント配線基盤等の電子部品の製造に有用である。 The present invention relates to an etching solution and an etching method for selectively etching titanium or a titanium alloy from a material containing titanium or a titanium alloy and other metals. The etching method of the present invention is useful for manufacturing electronic parts such as semiconductor products and printed wiring boards.
一般的にチタンまたはチタン合金のエッチング方法としては、フッ酸−硝酸混合液、フッ酸−過酸化水素混合液で処理する方法が知られている。前記の混合液では、錫および錫合金ならびにアルミニウムがエッチングされる。また、過酸化水素−アンモニア水−エチレンジアミン四酢酸（塩）混合液（特許文献１〜３参照）、過酸化水素−リン酸塩混合液（特許文献４参照）も知られているが、該混合液はチタンまたはチタン合金のエッチング速度が十分に満足するものではなく、かつ過酸化水素の分解が大きいため安定したエッチングが出来ない。従って、チタンまたはチタン合金を選択的にエッチングする方法の実用化が求められている。
本発明の目的は、チタンまたはチタン合金以外の金属、特に銅ならびに錫および錫合金さらにアルミニウム皮膜をエッチングせず、チタンまたはチタン合金皮膜を選択的にエッチングするためのエッチング方法を提供することである。 An object of the present invention is to provide an etching method for selectively etching a titanium or titanium alloy film without etching a metal other than titanium or a titanium alloy, particularly copper and tin and a tin alloy, and an aluminum film. .
本発明者らは鋭意検討を重ねた結果、過酸化水素、リン酸、ホスホン酸系化合物、アンモニアの水溶液で処理することで、銅、錫、錫合金およびアルミニウムをエッチングせず、チタンまたはチタン合金を選択的にエッチング出来ることを見出し、本発明を完成させるに至った。 As a result of intensive studies, the present inventors have processed copper and tin, tin alloys and aluminum without being etched by treating with an aqueous solution of hydrogen peroxide, phosphoric acid, phosphonic acid compounds and ammonia, and titanium or titanium alloys. As a result, the present invention has been completed.
すなわち、本発明は、下記に関するものである。
（１）エッチングされてはならない金属の存在下でチタンまたはチタン合金をエッチングするためのエッチング液であって、１０〜４０重量％の過酸化水素、０．０５〜５重量％のリン酸、０．００１〜０．１重量％のホスホン酸系化合物およびアンモニアからなる水溶液であるチタンまたはチタン合金皮膜のエッチング液。
（２）エッチングされてはならない金属の存在下でチタンまたはチタン合金をエッチングするためのエッチング液であって、１０〜４０重量％の過酸化水素、０．０５〜５重量％のリン酸、０．００１〜０．１重量％のホスホン酸系化合物およびアンモニアからなる水溶液で処理することを特徴とするチタンまたはチタン合金のエッチング方法。
That is, the present invention relates to the following.
(1) An etching solution for etching titanium or a titanium alloy in the presence of a metal that should not be etched, comprising 10 to 40% by weight of hydrogen peroxide, 0.05 to 5% by weight of phosphoric acid, 0 An etching solution for titanium or a titanium alloy film, which is an aqueous solution comprising 0.001 to 0.1% by weight of a phosphonic acid compound and ammonia.
(2) An etching solution for etching titanium or a titanium alloy in the presence of a metal that should not be etched, comprising 10 to 40 wt% hydrogen peroxide, 0.05 to 5 wt% phosphoric acid, 0 An etching method for titanium or a titanium alloy, characterized by treating with an aqueous solution comprising 0.001 to 0.1% by weight of a phosphonic acid compound and ammonia.
本発明のエッチング方法により、銅、錫、錫合金およびアルミニウムはエッチングせず、チタンまたはチタン合金を選択的にエッチングすることが出来る。 By the etching method of the present invention, copper, tin, tin alloy and aluminum are not etched, and titanium or titanium alloy can be selectively etched.
本発明の過酸化水素濃度は、１０〜４０重量％であり、好ましくは２０〜３０重量％である。濃度が１０重量％未満では十分なチタンおよびチタン合金のエッチング速度が得られず、また濃度が４０重量％を越えると安全性に問題が出てくるため好ましくない。 The hydrogen peroxide concentration of the present invention is 10 to 40% by weight, preferably 20 to 30% by weight. If the concentration is less than 10% by weight, a sufficient etching rate of titanium and a titanium alloy cannot be obtained, and if the concentration exceeds 40% by weight, there is a problem in safety, which is not preferable.
リン酸は、過酸化水素の安定剤としての効果と錫または錫合金に対して溶解抑制効果がある。濃度は、０．０５〜５重量％であり、好ましくは０．１〜１重量％である。濃度が０．０５重量％未満では過酸化水素の安定剤としての効果および錫または錫合金に対しての溶解抑制効果が十分ではなく、また濃度が５重量％を越えると銅、錫および錫合金がエッチングされるため好ましくない。 Phosphoric acid has an effect as a stabilizer of hydrogen peroxide and a dissolution inhibiting effect on tin or a tin alloy. The concentration is 0.05 to 5% by weight, preferably 0.1 to 1% by weight. When the concentration is less than 0.05% by weight, the effect of hydrogen peroxide as a stabilizer and the effect of inhibiting dissolution with respect to tin or tin alloy are not sufficient, and when the concentration exceeds 5% by weight, copper, tin and tin alloy Is not preferable because it is etched.
ホスホン酸系化合物としては、エチレンジアミンテトラ（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）、トリエチレンテトラミンヘキサ（メチレンホスホン酸）、プロパンジアミンテトラ（メチレンホスホン酸）、テトラエチレンペンタミンヘプタ（メチレンホスホン酸）、ヘキサメチレンテトラミンオクタ（メチレンホスホン酸）、ビス（ヘキサメチレン）トリアミンペンタ（メチレンホスホン酸）、１−ヒドロキシエチリデン−１，１−ジホスホン酸等が挙げられる。また、これらの化合物の有するホスホノメチル基の一部が水素原子やメチル基等の他の基に置換されたものであってもよい。これらのホスホン酸系化合物のホスホン酸基は、遊離の酸でなく例えばアンモニウム塩のような塩であってもよい。特に好ましいものは、ジエチレントリアミンペンタ（メチレンホスホン酸）、プロパンジアミンテトラ（メチレンホスホン酸）、１−ヒドロキシエチリデン−１，１−ジホスホン酸である。ホスホン酸系化合物は、過酸化水素の安定剤としての効果がある。濃度は、０．００１〜０．１重量％であり、好ましくは０．００５〜０．０２重量％である。０．００１重量％未満では、過酸化水素の安定剤としての効果が十分ではなく、また濃度が０．１重量％を越えると錫または錫合金がエッチングされるため好ましくない。 Examples of phosphonic acid compounds include ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), propanediaminetetra (methylenephosphonic acid), tetraethylenepentaminehepta (methylenephosphonic). Acid), hexamethylenetetramine octa (methylenephosphonic acid), bis (hexamethylene) triaminepenta (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid and the like. In addition, a part of the phosphonomethyl group of these compounds may be substituted with another group such as a hydrogen atom or a methyl group. The phosphonic acid group of these phosphonic acid compounds may be a salt such as an ammonium salt instead of a free acid. Particularly preferred are diethylenetriaminepenta (methylenephosphonic acid), propanediaminetetra (methylenephosphonic acid), and 1-hydroxyethylidene-1,1-diphosphonic acid. The phosphonic acid compound is effective as a hydrogen peroxide stabilizer. The concentration is 0.001 to 0.1% by weight, preferably 0.005 to 0.02% by weight. If it is less than 0.001% by weight, the effect of hydrogen peroxide as a stabilizer is not sufficient, and if the concentration exceeds 0.1% by weight, tin or a tin alloy is etched, which is not preferable.
アンモニアは、ｐＨ調整の目的で混合される。本発明のエッチング液のｐＨは、７〜９が好ましい。従って、過酸化水素、リン酸、ホスホン酸系化合物の混合液にアンモニア水を混合させてｐＨを７〜９に調整する。ｐＨが７未満では十分なチタンおよびチタン合金のエッチング速度が得られず、またｐＨが９を越えると過酸化水素の分解が促進されるため、および銅、アルミニウムがエッチングされるため好ましくない。 Ammonia is mixed for the purpose of pH adjustment. The pH of the etching solution of the present invention is preferably 7-9. Therefore, the pH is adjusted to 7 to 9 by mixing ammonia water in a mixed solution of hydrogen peroxide, phosphoric acid and phosphonic acid compound. If the pH is less than 7, a sufficient etching rate of titanium and titanium alloy cannot be obtained, and if the pH exceeds 9, decomposition of hydrogen peroxide is accelerated and copper and aluminum are etched, which is not preferable.
本発明のエッチング液と対象物との接触方法は、特に制限はなく、浸漬処理、スプレー処理等で行うことができる。処理温度は、３０〜６０℃が好ましい。処理温度が高いほどチタンおよびチタン合金のエッチング速度は向上するが、６０℃を越えると過酸化水素の分解が促進されるため好ましくない。また、本発明の処理時間に関しては、対象物の表面状態や形状に合わせて最適な時間を選択するが、実用的には１分〜１０分が好ましい。 The contact method between the etching solution of the present invention and the object is not particularly limited, and can be performed by immersion treatment, spray treatment, or the like. The treatment temperature is preferably 30 to 60 ° C. The higher the processing temperature is, the higher the etching rate of titanium and titanium alloy is. Moreover, regarding the processing time of the present invention, an optimal time is selected in accordance with the surface state and shape of the object, but practically 1 minute to 10 minutes is preferable.
以下に実施例及び比較例により、本発明を具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
実施例１
過酸化水素２０重量％、リン酸０．３重量％、ジエチレントリアミンペンタ（メチレンホスホン酸）０．０１重量％、アンモニア水を含有するｐＨ９．０に調整された水溶液であるエッチング液に、シリコンウェハー（ウェハー径：５インチ）上にスパッタ法でチタン膜を２０００Å成膜させた基盤とシリコンウェハー（ウェハー径：５インチ）上にスパッタ法で銅膜を２０００Å成膜させた基盤とシリコンウェハー（ウェハー径：５インチ）上にスパッタ法でアルミニウム膜を２０００Å成膜させた基盤と、更にＳＵＳ３０４材上に錫−鉛（６：４）電気メッキを１００００Å施した板（１００ｍｍ×１００ｍｍ×０．５ｍｍ）を４０℃で１分間浸漬させた。各種金属膜の溶解速度結果を表１に示す。
Example 1
A silicon wafer (20% by weight of hydrogen peroxide, 0.3% by weight of phosphoric acid, 0.01% by weight of diethylenetriaminepenta (methylenephosphonic acid), an aqueous solution containing aqueous ammonia and adjusted to pH 9.0 is added to a silicon wafer ( A substrate on which a titanium film is deposited by 2000 mm on a wafer diameter: 5 inches) and a silicon wafer (wafer diameter) on which a 2000 mm copper film is formed by sputtering on a silicon wafer (wafer diameter: 5 inches) : A 5 inch substrate with a 2000 mm aluminum film formed by sputtering and a SUS304 material with a tin-lead (6: 4) electroplated plate with 10,000 mm (100 mm x 100 mm x 0.5 mm) It was immersed at 40 ° C. for 1 minute. Table 1 shows the dissolution rate results of various metal films.
実施例２
過酸化水素３０重量％、リン酸０．２重量％、プロパンジアミンテトラ（メチレンホスホン酸）０．００５重量％、アンモニア水を含有するｐＨ８．５に調整されたエッチング液を用いる以外は実施例１と同様に行った。結果を表１に示す。
Example 2
Example 1 except that an etching solution adjusted to pH 8.5 containing 30% by weight of hydrogen peroxide, 0.2% by weight of phosphoric acid, 0.005% by weight of propanediaminetetra (methylenephosphonic acid), and aqueous ammonia is used. As well as. The results are shown in Table 1.
実施例３
過酸化水素３５重量％、リン酸０．１重量％、１−ヒドロキシエチリデン−１，１−ジホスホン酸０．０１重量％、アンモニア水を含有するｐＨ８．０に調整されたエッチング液を用いる以外は実施例１と同様に行った。結果を表１に示す。
Example 3
Except for using an etching solution adjusted to pH 8.0 containing hydrogen peroxide 35% by weight, phosphoric acid 0.1% by weight, 1-hydroxyethylidene-1,1-diphosphonic acid 0.01% by weight, and aqueous ammonia. The same operation as in Example 1 was performed. The results are shown in Table 1.
比較例１
硝酸１重量％、フッ酸１重量％を含有するエッチング液を用いる以外は実施例１と同様に行った。結果を表１に示す。
Comparative Example 1
The same operation as in Example 1 was performed except that an etching solution containing 1% by weight of nitric acid and 1% by weight of hydrofluoric acid was used. The results are shown in Table 1.
比較例２
過酸化水素１重量％、フッ酸１重量％含有するエッチング液を用いる以外は実施例１と同様に行った。結果を表１に示す。
Comparative Example 2
The same procedure as in Example 1 was performed except that an etching solution containing 1% by weight of hydrogen peroxide and 1% by weight of hydrofluoric acid was used. The results are shown in Table 1.
比較例３
過酸化水素２０重量％、エチレンジアミン四酢酸四ナトリウム０．１重量％、アンモニア水を含有するｐＨ８．０に調整されたエッチング液を用いる以外は実施例１と同様に行った。結果を表１に示す。
Comparative Example 3
The same procedure as in Example 1 was performed except that an etching solution adjusted to pH 8.0 containing 20% by weight of hydrogen peroxide, 0.1% by weight of ethylenediaminetetraacetic acid tetrasodium, and aqueous ammonia was used. The results are shown in Table 1.
比較例４
過酸化水素２０重量％、リン酸水素二ナトリウムを含有するｐＨ８．０に調整されたエッチング液を用いる以外は実施例１と同様に行った。結果を表１に示す。
Comparative Example 4
The same procedure as in Example 1 was performed except that an etching solution adjusted to pH 8.0 containing 20% by weight of hydrogen peroxide and disodium hydrogen phosphate was used. The results are shown in Table 1.
比較例５
アンモニアの代わりに水酸化カリウムを用いた以外は、実施例１と同様に行った。結果を表１に示す。
Comparative Example 5
The same procedure as in Example 1 was performed except that potassium hydroxide was used instead of ammonia. The results are shown in Table 1.
比較例６
アンモニアの代わりに水酸化テトラメチルアンモニウムを用いた以外は、実施例１と同様に行った。結果を表１に示す。
Comparative Example 6
The same procedure as in Example 1 was performed except that tetramethylammonium hydroxide was used instead of ammonia. The results are shown in Table 1.
実施例４
過酸化水素２０重量％、リン酸０．２重量％、ジエチレントリアミンペンタ（メチレンホスホン酸）０．０１重量％、アンモニア水を含有するｐＨ８．０に調整されたエッチング液に金属チタン１００ｍｇ／Ｌを溶解させ、液温度を４０℃に保ち８時間放置させた。放置前と放置後の過酸化水素の分解率を表２に示す。
過水分解率（％）＝（放置前過水濃度−放置後過水濃度）×１００／放置前過水濃度
Example 4
Dissolve 100 mg / L of titanium metal in an etching solution adjusted to pH 8.0 containing 20 wt% hydrogen peroxide, 0.2 wt% phosphoric acid, 0.01 wt% diethylenetriaminepenta (methylenephosphonic acid), and aqueous ammonia. The liquid temperature was kept at 40 ° C. and left for 8 hours. Table 2 shows the decomposition rate of hydrogen peroxide before and after standing.
Overwater decomposition rate (%) = (overwater concentration before leaving-overwater concentration after leaving) x 100 / overwater concentration before leaving
比較例７
過酸化水素２０重量％、エチレンジアミン四酢酸四ナトリウム０．１重量％、アンモニア水を含有するｐＨ８．０に調整されたエッチング液を用いる以外は実施例４と同様に行った。結果を表２に示す。
Comparative Example 7
The same operation as in Example 4 was performed except that an etching solution adjusted to pH 8.0 containing 20% by weight of hydrogen peroxide, 0.1% by weight of ethylenediaminetetraacetic acid tetrasodium, and aqueous ammonia was used. The results are shown in Table 2.
比較例８
過酸化水素２０重量％、リン酸水素二ナトリウムを含有するｐＨ８．０に調整されたエッチング液を用いる以外は実施例４と同様に行った。結果を表２に示す。
Comparative Example 8
The same procedure as in Example 4 was performed except that an etching solution adjusted to pH 8.0 containing 20% by weight of hydrogen peroxide and disodium hydrogen phosphate was used. The results are shown in Table 2.
表１に示されるように、本発明のエッチング方法により銅ならびに錫および錫合金さらにアルミニウムはエッチングせず、チタンまたはチタン合金皮膜を選択的にエッチング出来る。 As shown in Table 1, the etching method of the present invention can selectively etch titanium or a titanium alloy film without etching copper, tin, a tin alloy, and aluminum.
表２に示されるように、本発明のエッチング方法は過酸化水素の分解を抑制しているため、安定したチタンまたはチタン合金エッチングを行うことが出来る。 As shown in Table 2, since the etching method of the present invention suppresses decomposition of hydrogen peroxide, stable titanium or titanium alloy etching can be performed.
Claims (5)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004141438A JP4471094B2 (en) | 2004-05-11 | 2004-05-11 | Titanium or titanium alloy etchant |
| TW094114625A TWI360586B (en) | 2004-05-11 | 2005-05-06 | Etching solution for titanium or titanium alloy |
| KR1020050038699A KR101154762B1 (en) | 2004-05-11 | 2005-05-10 | Etching solution for titanium or titanium alloy |
| CNB2005100688258A CN100526507C (en) | 2004-05-11 | 2005-05-11 | Etching liquid fot titanium or titanium alloy |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2004141438A JP4471094B2 (en) | 2004-05-11 | 2004-05-11 | Titanium or titanium alloy etchant |
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| JP2005320608A true JP2005320608A (en) | 2005-11-17 |
| JP4471094B2 JP4471094B2 (en) | 2010-06-02 |
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| JP (1) | JP4471094B2 (en) |
| KR (1) | KR101154762B1 (en) |
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Cited By (5)
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| JP2010037590A (en) * | 2008-08-04 | 2010-02-18 | Ulvac Japan Ltd | Method for manufacturing component in vacuum chamber, method for reconditioning the component, method for manufacturing substrate-transporting tray and method for reconditioning substrate-transporting tray |
| EP2234145A1 (en) * | 2007-12-21 | 2010-09-29 | Wako Pure Chemical Industries, Ltd. | Etching agent, etching method and liquid for preparing etching agent |
| US8300167B2 (en) | 2007-06-14 | 2012-10-30 | Sharp Kabushiki Kaisha | Display panel, display device, and method for manufacturing display panel |
| WO2015002272A1 (en) * | 2013-07-05 | 2015-01-08 | 和光純薬工業株式会社 | Etching agent, etching method and etching agent preparation liquid |
| US10155903B2 (en) | 2014-06-23 | 2018-12-18 | Samsung Electronics Co., Ltd. | Metal etchant compositions and methods of fabricating a semiconductor device using the same |
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| KR20120067198A (en) * | 2010-12-15 | 2012-06-25 | 제일모직주식회사 | Etching paste and method for preparing thereof, method of forming a pattern 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 |
| TWI808965B (en) | 2017-03-31 | 2023-07-21 | 日商關東化學股份有限公司 | Etching liquid composition and etching method for ti layer or ti-containing layer |
| 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 |
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| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100497835B1 (en) * | 1997-01-27 | 2005-09-08 | 미쓰비시 가가꾸 가부시키가이샤 | Surface treatment composition and method for treating surface of substrate by using rhe same |
| JPWO2003031688A1 (en) * | 2001-10-09 | 2005-01-27 | ナガセケムテックス株式会社 | Etching solution composition |
| TWI245071B (en) * | 2002-04-24 | 2005-12-11 | Mitsubishi Chem Corp | Etchant and method of etching |
| JP2003328159A (en) | 2002-05-02 | 2003-11-19 | Mitsubishi Gas Chem Co Inc | Surface treatment agent |
-
2004
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- 2005-05-06 TW TW094114625A patent/TWI360586B/en active
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8300167B2 (en) | 2007-06-14 | 2012-10-30 | Sharp Kabushiki Kaisha | Display panel, display device, and method for manufacturing display panel |
| EP2234145A1 (en) * | 2007-12-21 | 2010-09-29 | Wako Pure Chemical Industries, Ltd. | Etching agent, etching method and liquid for preparing etching agent |
| EP2234145A4 (en) * | 2007-12-21 | 2011-12-07 | Wako Pure Chem Ind Ltd | Etching agent, etching method and liquid for preparing etching agent |
| US8513139B2 (en) | 2007-12-21 | 2013-08-20 | Wako Pure Chemical Industries, Ltd. | Etching agent, etching method and liquid for preparing etching agent |
| US8871653B2 (en) | 2007-12-21 | 2014-10-28 | Wako Pure Chemical Industries, Ltd. | Etching agent, etching method and liquid for preparing etching agent |
| JP2010037590A (en) * | 2008-08-04 | 2010-02-18 | Ulvac Japan Ltd | Method for manufacturing component in vacuum chamber, method for reconditioning the component, method for manufacturing substrate-transporting tray and method for reconditioning substrate-transporting tray |
| WO2015002272A1 (en) * | 2013-07-05 | 2015-01-08 | 和光純薬工業株式会社 | Etching agent, etching method and etching agent preparation liquid |
| KR20160029094A (en) | 2013-07-05 | 2016-03-14 | 와코 쥰야꾸 고교 가부시키가이샤 | Etching agent, etching method and etching agent preparation liquid |
| US9845538B2 (en) | 2013-07-05 | 2017-12-19 | Wako Pure Chemical Industries, Ltd. | Etching agent, etching method and etching agent preparation liquid |
| US10155903B2 (en) | 2014-06-23 | 2018-12-18 | Samsung Electronics Co., Ltd. | Metal etchant compositions and methods of fabricating a semiconductor device using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1706986A (en) | 2005-12-14 |
| KR101154762B1 (en) | 2012-06-18 |
| TW200606280A (en) | 2006-02-16 |
| KR20060045996A (en) | 2006-05-17 |
| JP4471094B2 (en) | 2010-06-02 |
| TWI360586B (en) | 2012-03-21 |
| CN100526507C (en) | 2009-08-12 |
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