CN1706986A - Etching liquid fot titanium or titanium alloy - Google Patents

Etching liquid fot titanium or titanium alloy Download PDF

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Publication number
CN1706986A
CN1706986A CNA2005100688258A CN200510068825A CN1706986A CN 1706986 A CN1706986 A CN 1706986A CN A2005100688258 A CNA2005100688258 A CN A2005100688258A CN 200510068825 A CN200510068825 A CN 200510068825A CN 1706986 A CN1706986 A CN 1706986A
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titanium
weight
etching
etching solution
hydrogen peroxide
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CN100526507C (en
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高桥健一
细见彰良
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00Etching, surface-brightening or pickling compositions
    • C09K13/04Etching, surface-brightening or pickling compositions containing an inorganic acid
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-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
    • C23F1/00Etching metallic material by chemical means
    • C23F1/10Etching compositions
    • C23F1/14Aqueous compositions
    • C23F1/16Acidic compositions
    • C23F1/30Acidic compositions for etching other metallic material
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned

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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)
  • Inorganic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

The invention provides an etching solution and etching method for selectively etching titanium or a titanium alloy which can not etch the the metal which must not be etched, for example copper, tin, tin alloy and aluminum. The etching solution comprising 10 to 40 wt.% of hydrogen peroxide, 0.05 to 5 wt.% of phosphoric acid, 0.001 to 0.1 wt.% of phosphonic-acid-based compound, and ammonia.

Description

Titanium or titanium alloy etching solution
Technical field
The present invention relates on the etch target thing that contains titanium or titanium alloy and metal in addition thereof the etching solution and the engraving method of etching titanium optionally or titanium alloy.Etching solution of the present invention and engraving method are used for the manufacturing of electron devices such as semiconductor article, printed wiring board.
Background technology
As the general titanium or the engraving method of titanium alloy, known have, by the method for hydrofluoric acid-nitric acid mixing solutions, hydrofluoric acid-hydrogen peroxide mixed solution processing.Aforesaid mixed solution is the tin of etching simultaneously, tin alloy and aluminium also.In addition, known hydrogen peroxide-ammoniacal liquor-ethylenediamine tetraacetic acid (EDTA) (salt) mixed solution (with reference to patent documentation 1~3) in addition, hydrogen peroxide-phosphoric acid salt mixed solution (with reference to patent documentation 4), but this mixed solution is insufficient to the etching speed of titanium or titanium alloy, and, can not stably carry out etching because the decomposition of hydrogen peroxide is obvious.Therefore, wish to develop the etching solution and the engraving method of a kind of optionally etching titanium or titanium alloy.
Patent documentation 1 spy opens flat 8-13166 communique
Patent documentation 2 spies open flat 8-53781 communique
No. 4554050 communique of patent documentation 3 United States Patent (USP)s
Patent documentation 4 spies open the 2000-311891 communique
Summary of the invention
System of the present invention aims to provide the metal beyond a kind of not etching titanium or the titanium alloy, particularly not etch copper, tin, tin alloy and aluminium, and be used for the etching solution and the engraving method of etching titanium optionally or titanium alloy.
Present inventors found that through conscientious repeatedly research: the aqueous solution that contains hydrogen peroxide, phosphoric acid, phosphonic acids based compound, ammonia is etch copper, tin, tin alloy and aluminium not, and optionally etching titanium or titanium alloy have been finished the present invention thus.
That is, the present invention relates to following content.
(1) a kind of be used for have can not etched metal in the presence of, the etching solution of etching titanium or titanium alloy optionally, it is characterized in that: it is a kind of hydrogen peroxide of 10~40 weight %, the phosphoric acid of 0.05~5 weight %, the phosphonic acids based compound of 0.001~0.1 weight % and aqueous solution of ammonia of containing.
(2) method of a kind of optionally etching titanium or titanium alloy, it is characterized in that: make contain can not etched metal and, the etch target thing of titanium or titanium alloy, contact with the phosphoric acid of the hydrogen peroxide that contains 10~40 weight %, 0.05~5 weight %, the phosphonic acids based compound of 0.001~0.1 weight % and the aqueous solution of ammonia.
By etching solution of the present invention and engraving method, not etch copper, tin, tin alloy and aluminium, and optionally etching titanium or titanium alloy.
Embodiment
In etching solution of the present invention, concentration of hydrogen peroxide is 10~40 weight %, preferred 20~30 weight %.If concentration less than 10 weight %, then the etching speed of titanium or titanium alloy is not enough, and is if surpass the problem that 40 weight % then have the security aspect, therefore not preferred.
Phosphoric acid plays the effect of the stablizer of hydrogen peroxide, suppresses the effect of the dissolving (etching) of tin or tin alloy in addition.The concentration of phosphoric acid in etching solution is 0.05~5 weight %, preferred 0.1~1 weight %.If concentration less than 0.05 weight % is then as the effect of the stablizer of hydrogen peroxide with to suppress the effect of dissolving (etching) of tin or tin alloy insufficient.Then copper, tin and tin alloy can be etched if concentration surpasses 5 weight %, and be therefore not preferred.
As the phosphonic acids based compound, can enumerate ethylenediamine tetraacetic (methylene phosphonic acid), diethylenetriamine five (methylene phosphonic acid), Triethylenetetramine (TETA) six (methylene phosphonic acid), propylene diamine four (methylene phosphonic acid), tetren seven (methylene phosphonic acid), vulkacit H eight (methylene phosphonic acid), two (hexa-methylene) triamine five (methylene phosphonic acids), 1-hydroxy ethylidene-1, the 1-di 2 ethylhexyl phosphonic acid.In addition, a part of (phosphonomethyl) that these compounds had can be replaced by other group such as hydrogen atom or methyl.The phosphonate group of these phosphonic acids based compounds can be a free acid, for example the salt of ammonium salt etc.Preferred especially diethylenetriamine five (methylene phosphonic acid), propylene diamine four (methylene phosphonic acid), 1-hydroxy ethylidene-1, the 1-di 2 ethylhexyl phosphonic acid.The phosphonic acids based compound has the effect as the stablizer of hydrogen peroxide.Concentration in the etching solution is 0.001~0.1 weight %, preferred 0.005~0.02 weight %.The less than 0.001 weight % then effect as the stablizer of hydrogen peroxide is not enough.Then tin or tin alloy can be etched if surpass 0.1 weight %, and be therefore not preferred.
The purpose of mixing ammonia is to adjust the pH of etching solution.The pH of etching solution of the present invention preferred 7~9.Therefore, the consumption of ammonia is to make the pH of the aqueous solution that contains hydrogen peroxide, phosphoric acid, phosphonic acids based compound be adjusted to 7~9 amount.If the etching speed of 7 titaniums of pH less than and titanium alloy is not enough, if in addition pH decomposition that can promote hydrogen peroxide above 9, and copper and aluminium can be etched, so not preferred.
Etching solution can followingly be made: for example add hydrogen peroxide, phosphoric acid, phosphonic acids based compound in water, stir and to obtain the aqueous solution, further add ammoniacal liquor, adjust pH to 7~9 of the aqueous solution and make.
Engraving method of the present invention is undertaken by the etch target thing is contacted with etching solution.Contact method has no particular limits, and can be undertaken by dip treating, spraying processing etc.Preferred 30~60 ℃ of treatment temp.Though the high more etching speed that can promote titanium and titanium alloy more of treatment temp is if the decomposition that then can promote hydrogen peroxide above 60 ℃ is therefore not preferred.In addition, disposing time can be selected the optimal time according to the condition of surface and the shape of etch target thing, preferred in actual applications 1~10 minute.
Embodiment
By the following examples and comparative example, specifically describe the present invention, but the present invention is not subjected to the qualification of following examples.
Embodiment 1
Containing 20 weight % hydrogen peroxide, 0.3 weight % phosphoric acid, 0.01 weight % diethylenetriamine, five (methylene phosphonic acid) and ammonia, pH is adjusted in 9.0 the aqueous solution (etching solution), at 40 ℃ of following each substrates of dipping 1 minute down.
(1) goes up the substrate that forms the titanium film of thick 2000 by sputtering method at silicon wafer (wafer diameter: 5 inches)
(2) go up the substrate that forms the copper film of thick 2000 by sputtering method at silicon wafer (wafer diameter: 5 inches)
(3) go up the substrate that forms the aluminium film of thick 2000 by sputtering method at silicon wafer (wafer diameter: 5 inches)
(4) on the SUS304 material, form the substrate (100mm * 100mm * 0.5mm) of tin-lead (6:4) electroplating film of thick 10000
The dissolution rate of various metallic membranes is as shown in table 1.
Embodiment 2
Except use contains 30 weight % hydrogen peroxide, 0.2 weight % phosphonic acids, 0.005 weight % propylene diamine, four (methylene phosphonic acid) and ammonia, pH is adjusted to beyond 8.5 the etching solution, and all the other carry out according to method similarly to Example 1.The result is as shown in table 1.
Embodiment 3
Except use contains the 1-hydroxy ethylidene-1 of 35 weight % hydrogen peroxide, 0.1 weight % phosphonic acids, 0.01 weight %, 1-di 2 ethylhexyl phosphonic acid and ammonia, pH are adjusted to beyond 8.0 the etching solution, and all the other carry out according to method similarly to Example 1.The result is as shown in table 1.
Comparative example 1
Except use contained the aqueous solution (etching solution) of 1 weight % nitric acid, 1 weight % hydrofluoric acid, all the other carried out according to method similarly to Example 1.The result is as shown in table 1.
Comparative example 2
Except use contained the aqueous solution (etching solution) of 1 weight % hydrogen peroxide, 1 weight % hydrofluoric acid, all the other carried out according to method similarly to Example 1.The result is as shown in table 1.
Comparative example 3
Except use contains 20 weight % hydrogen peroxide, 0.1 weight % tetrasodium ethylenediamine tetraacetate and ammonia, pH is adjusted to 8.0 the aqueous solution (etching solution) in addition, and all the other carry out according to method similarly to Example 1.The result is as shown in table 1.
Comparative example 4
Be adjusted to 8.0 the aqueous solution (etching solution) except use contains 20 weight % hydrogen peroxide, Sodium phosphate dibasic, pH, all the other carry out according to method similarly to Example 1.The result is as shown in table 1.
Comparative example 5
Except replace ammonia with potassium hydroxide, all the other carry out according to method similarly to Example 1.The result is as shown in table 1.
Comparative example 6
Except replace ammonia with tetramethyl ammonium hydroxide, all the other carry out according to method similarly to Example 1.The result is as shown in table 1.
Embodiment 4
Containing 20 weight % hydrogen peroxide, 0.2 weight % phosphoric acid, 0.01 weight % diethylenetriamine, five (methylene phosphonic acid) and ammonia, pH is adjusted in 8.0 the etching solution, and with 100mg/L dissolution of metals titanium, the liquid temperature remains on 40 ℃ and placed 8 hours.Before placing and the rate of decomposition of the hydrogen peroxide after placing as shown in table 2.
Concentration of hydrogen peroxide before rate of decomposition (%)=place (concentration of hydrogen peroxide before placing-placement back concentration of hydrogen peroxide) * 100/
Comparative example 7
Except use contains 20 weight % hydrogen peroxide, 0.1 weight % tetrasodium ethylenediamine tetraacetate and ammonia, pH is adjusted to 8.0 the aqueous solution (etching solution), all the other carry out according to method similarly to Example 4.The result is as shown in table 2.
Comparative example 8
Be adjusted to 8.0 the aqueous solution (etching solution) except use contains 20 weight % hydrogen peroxide, Sodium phosphate dibasic, pH, all the other carry out according to method similarly to Example 4.The result is as shown in table 2.
[table 1]
Meltage (/minute)
Titanium Copper Aluminium Tin-lead
Embodiment 1 ?1500 <10 <10 <10
Embodiment 2 ?1700 <10 <10 <10
Embodiment 3 ?1800 <10 <10 <10
Comparative example 1 ?1000 1000 2000 3000
Comparative example 2 ?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
As shown in table 1, etching solution of the present invention can etch copper, tin, tin alloy and aluminium, optionally etching titanium or titanium alloy.
[table 2]
The hydrogen peroxide decomposition rate
Embodiment 4 ?<1%
Comparative example 7 ?20%
Comparative example 8 ?30%
As shown in table 2 because etching solution of the present invention has suppressed the decomposition of hydrogen peroxide, therefore can be stably optionally etching titanium or titanium alloy.

Claims (7)

1. etching solution, its be used for have can not etched metal in the presence of, optionally the etching solution of etching titanium or titanium alloy is characterized in that: contain the hydrogen peroxide of 10~40 weight %, the phosphoric acid of 0.05~5 weight %, the phosphonic acids based compound of 0.001~0.1 weight % and the aqueous solution of ammonia.
2. the etching solution of claim 1 record, it is characterized in that: described can not etched metal be at least a kind of metal that is selected from copper, tin, tin alloy and the aluminium.
In the claim 1 or 2 record etching solution, it is characterized in that: pH is adjusted into 7~9.
4. the etching solution of record in the claim 1 or 2 is characterized in that: contain the ammonia that the pH that makes etching solution is adjusted into 7~9 amount.
5. the etching solution of record in the claim 1 or 2 is characterized in that: the phosphonic acids based compound is for being selected from diethylenetriamine five (methylene phosphonic acid), propylene diamine four (methylene phosphonic acid), 1-hydroxy ethylidene-1, in the 1-di 2 ethylhexyl phosphonic acid at least a kind.
6. method of etching titanium or titanium alloy optionally, it is characterized in that: make contain can not etched metal and, the etch target thing of titanium or titanium alloy, contact with the phosphoric acid of the hydrogen peroxide that contains 10~40 weight %, 0.05~5 weight %, the phosphonic acids based compound of 0.001~0.1 weight % and the aqueous solution of ammonia.
7. the engraving method of claim 6 record, it is characterized in that: described can not etched metal be at least a kind of metal that is selected from copper, tin, tin alloy and the aluminium.
CNB2005100688258A 2004-05-11 2005-05-11 Etching liquid fot titanium or titanium alloy Active CN100526507C (en)

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JP2004141438A JP4471094B2 (en) 2004-05-11 2004-05-11 Titanium or titanium alloy etchant
JP2004141438 2004-05-11

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CN103210058A (en) * 2010-12-15 2013-07-17 第一毛织株式会社 Etching paste, a production method therefor and a pattern forming method using the same
CN107075694A (en) * 2014-09-19 2017-08-18 三菱电机株式会社 The manufacture method of semiconductor device
CN110581061A (en) * 2019-09-25 2019-12-17 同辉电子科技股份有限公司 Processing technology of gallium nitride MMIC power amplifier chip
CN114196956A (en) * 2020-09-18 2022-03-18 珠海市丹尼尔电子科技有限公司 Etching solution for titanium

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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
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
US20150368557A1 (en) 2014-06-23 2015-12-24 Hyosan Lee Metal etchant compositions and methods of fabricating a semiconductor device using the same
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US10865484B2 (en) 2016-03-29 2020-12-15 Technic France Solution and method for etching titanium based materials
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JP2003328159A (en) 2002-05-02 2003-11-19 Mitsubishi Gas Chem Co Inc Surface treatment agent

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CN103210058A (en) * 2010-12-15 2013-07-17 第一毛织株式会社 Etching paste, a production method therefor and a pattern forming method using the same
CN107075694A (en) * 2014-09-19 2017-08-18 三菱电机株式会社 The manufacture method of semiconductor device
CN110581061A (en) * 2019-09-25 2019-12-17 同辉电子科技股份有限公司 Processing technology of gallium nitride MMIC power amplifier chip
CN114196956A (en) * 2020-09-18 2022-03-18 珠海市丹尼尔电子科技有限公司 Etching solution for titanium
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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KR20060045996A (en) 2006-05-17
KR101154762B1 (en) 2012-06-18
JP4471094B2 (en) 2010-06-02
TWI360586B (en) 2012-03-21
CN100526507C (en) 2009-08-12
JP2005320608A (en) 2005-11-17

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