CN1324164C - Copper or copper alloy corrodent and corrosion method - Google Patents
Copper or copper alloy corrodent and corrosion method Download PDFInfo
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- CN1324164C CN1324164C CNB021222509A CN02122250A CN1324164C CN 1324164 C CN1324164 C CN 1324164C CN B021222509 A CNB021222509 A CN B021222509A CN 02122250 A CN02122250 A CN 02122250A CN 1324164 C CN1324164 C CN 1324164C
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Abstract
The present invention provides an etching agent for copper or a copper alloy, which consists of an aqueous solution containing hydroxyl amine, an oxidizer, ammonium salt, and an azole compound, for smoothening the surface of copper under a mild condition.
Description
Technical field
The present invention relates to be level and smooth etching reagent and caustic solution with the surface corrosion of copper or copper alloy (following simply be called ' copper ').
Background technology
As the etching reagent that can form level and smooth copper surface, for example, in the fair 58-21028 communique of spy the acidic aqueous solution that contains oxalate, hydrogen peroxide, amine and benzotriazole is disclosed.And, the acidic aqueous solution that contains sulfuric acid, hydrogen peroxide and stabilizer of hydrogen peroxide is disclosed in No. 5630950 detailed book of United States Patent (USP).
Yet for the etching reagent of the open 58-21028 communique of spy, existence must handle under 50 ℃ high temperature, and separate out the problem of the cupric coordination compound etc. of insoluble easily.In addition, for the etching reagent of No. the 5630950th, United States Patent (USP), existence must be at narrow scope control sulfuric acid concentration or concentration of hydrogen peroxide, and because concentration of hydrogen peroxide is easy to generate the problem of unexpected boiling etc. when too high.
Summary of the invention
Therefore, in order to solve the shortcoming of prior art, the object of the present invention is to provide a kind of caustic solution that under the condition of gentleness, makes the etching reagent of copper surface smoothing and make above-mentioned surface smoothing.
In order to address the above problem, the inventor found that through deep repeatedly research: if the copper surface is contacted with the aqueous solution that contains azanol, oxygenant, ammonium salt and azole compounds, just can make the copper surface smoothing.
That is, the present invention is finished by following forming.
(1) constitutes the etching reagent of copper or copper alloy by the aqueous solution that contains azanol, oxygenant, ammonium salt and azole compounds.
(2) aqueous solution that contains azanol, oxygenant, ammonium salt and azole compounds is contacted with the surface of copper or copper alloy and make the caustic solution of above-mentioned surface smoothing.
Embodiment
Below, describe the present invention in detail.
Employed azanol is to make solution keep alkalescence among the present invention, the inhibited oxidation agent is decomposed, and in solution, keep the composition of copper, as its concrete example, for example can list: Monoethanolamine MEA BASF, the N-Mono Methyl Ethanol Amine, the N-ehtylethanolamine, the N-butylethanolamine, N, the N-dimethylethanolamine, N, the N-diethylethanolamine, the Monoethanolamine MEA BASF class of 2-(2-hydroxyl) ethoxy ethanol amine etc., diethanolamine, N methyldiethanol amine, the diethanol amine of N butyl diethanol amine etc., trolamine, Propanolamine, Yi Bingchunan, the alkanol amine of hydroxyethyl piperazine etc., or ammonia soln.
Among above-mentioned azanol, from the ability height that keeps copper and obtain easily, on this aspect of low price, preferably the carbonatoms of Monoethanolamine MEA BASF, diethanolamine, trolamine etc. is at alkanolamine below 8 or ammonia soln etc.Above-mentioned azanol also can share more than 2 kinds.
The concentration of the azanol in the etching reagent is preferably 1-40% (weight %, below identical), more preferably 5-30%.
In above-mentioned concentration is under the situation of 1-40%, and the amount of the soluble copper of corrosive fluid is more, and oxygenant is difficult to decompose, and also better from the cost aspect.
Employed oxygenant is to be used for making the copper oxidation and to promote it to be dissolved to the composition of solution among the present invention, as its concrete example, for example can list: chloric acid, oxymuriate (sodium salt, sylvite etc.), chlorous acid, chlorite (sodium salt, sylvite etc.), hypochlorous acid, hypochlorite (sodium salt, sylvite etc.) are among above-mentioned oxygenant, the salt of preferred oxymuriate, chlorite, hypochlorite etc., this is because their stable higher in solution.Above-mentioned oxygenant also can share more than 2 kinds.
The preferred 1-15% of the concentration of the oxygenant in the etching reagent, more preferably 5-10%.
At above-mentioned solution is under the situation of 1-15%, can accelerate corrosion speed, and oxygenant itself is difficult to decompose, and also better from the cost aspect.
Employed ammonium salt is by supply with the composition that ammonium ion promotes copper dissolution in solution among the present invention, as its concrete example, for example can list: ammonium chloride, brometo de amonio, ammonium sulfate, ammonium persulphate, Ammonium sulfamate, ammonium oxalate, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium citrate, dibasic ammonium citrate, ammonium adipate, DL-Lactic acid ammonium salt.
Among above-mentioned ammonium salt, from reactive low, this aspect of security that can improve solution of oxygenant on, preferred ammonium chloride, brometo de amonio, ammonium sulfate, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium citrate.Above-mentioned ammonium salt also can share more than 2 kinds.
The concentration of the ammonium salt in the etching reagent is preferably 1～10%, and more preferably 2～6%.Be that corrosion speed can be not too fast under 1～10% the situation in above-mentioned concentration, can be not slow excessively, more moderate yet, therefore, can not cause depth inequality, obtain level and smooth copper surface easily.
Employed azole compounds is the dissolving that suppresses the copper of vertical direction among the present invention, promote the dissolved composition of the copper of horizontal direction, as its concrete example, for example can list: imidazoles, the 2-phenylimidazole, the 1-vinyl imidazole, benzoglyoxaline, 2-butyl benzoglyoxaline, 2-styroyl benzoglyoxaline, the amino benzoglyoxaline of 2-, the imidazoles of 2-mercaptobenzimidazole etc., 1,2, the 4-triazole, 3-amino-1,2, the 4-triazole, 1,2, the 3-benzotriazole, I-hydroxybenzotriazole, carboxyl benzotriazole, Deng triazole species, tetrazolium, 5-phenyl-1H-tetrazolium, 5-methyl isophthalic acid H-tetrazolium, the tetrazolium class of 5-amino-1H-tetrazolium etc., the pyrrole miaow, benzothiazole, 2-mercaptobenzothiazole etc.
Among above-mentioned azole compounds, preferred imidazoles, 1-vinyl imidazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, I-hydroxybenzotriazole, tetrazolium, 5-methyl isophthalic acid H-tetrazolium, 5-amino-1H-tetrazolium etc. do not have a substituent azole compounds of aromatic series, this is because they are soluble in the solution, and it is level and smooth respond well that the copper surface is become.Above-mentioned azole compounds also can share more than 2 kinds.
The concentration of the azole compounds in the etching reagent is preferably 0.1～2%, and more preferably 0.4～1.2%.Be under 0.1～2% the situation, to obtain level and smooth copper surface easily in above-mentioned concentration.
Etching reagent of the present invention is an alkalescence, and the pH value is generally 10～12 scope.
Can also in etching reagent of the present invention, allocate various additives into, for example,, also can allocate tensio-active agent in order to make more homogenizing of etching reagent.
By each above-mentioned composition is dissolved in water, can adjust etching reagent of the present invention at an easy rate.For above-mentioned water, preferred ion exchanged water etc. are the water of deionizing material and impurity.
Having no particular limits for the copper surface of adopting etching reagent of the present invention to handle, for example can be the surface of Copper Foil, electrolytic copper free plated film, electrolytic copper plated film, copper sputtered films of bismuth etc.For above-mentioned copper surface, preferred to carry out alkali cleaning by aqueous sodium hydroxide solution etc. clean or carry out the clean clean Surface of pickling by sulfuric acid or hydrochloric acid.
As the method that makes etching reagent of the present invention contact copper surface, for example can use gunite, spraying process, pickling process etc., wash then, drying.
Condition when etching reagent and copper surface are contacted is not particularly limited, but preferred 20～30 ℃ of the temperature of etching reagent usually, duration of contact in preferred 30～120 seconds.
And the preferable range of etching extent (depth of corrosion) is with the difference of the smoothness of the condition of surface on copper surface or target and difference, normally 1～4 μ m.
If adopt etching reagent of the present invention to corrode the copper surface,, can improve the smoothness on copper surface along with corrosive carries out.Therefore, when processed concavo-convex big or when wanting to obtain high surperficial of smoothness, can increase etching extent (depth of corrosion).
As previously discussed, the etching reagent of the application of the invention corrodes the copper surface, the copper surface corrosion can be got very level and smooth.Etching reagent of the present invention helps pre-treatment of for example nickel plating, gold-plated, silver-plated, zinc-plated etc. metallizing etc., can improve the smoothness of metallizing.And, the pre-treatment of the stickup photoresists under the situations such as copper circuit pattern that also help adopting photo-engraving process to form printed circuit board (PCB) etc.
[embodiment]
Embodiment 1～6 and comparative example 1～2
Composition shown in the mixture table 1, the modulation etching reagent.
Then, the use in printed circuit board copper clad laminate be impregnated in 5% the aqueous hydrochloric acid, dipping time was 15 seconds, washed then, drying, cleaned the copper surface.Under 25 ℃, spray the etching reagent shown in the following table 1, the time was 30 seconds, corroded 2 μ m, washed then, drying.And, calculate the value of etching extent according to weight, surface-area and the proportion of the copper that dissolves.
Adopt the smoothness on the copper surface after the glossiness evaluation is handled.
Glossiness is to use the portable gloss degree meter PG-1M of Japanese electric look industry (strain) system and connects according to JIS Z 8741 mensuration 20 degree specular glosss and obtains.Show the result in the table 1.
Comparative example 1
Identical with embodiment 1, the modulation etching reagent, and corrode, but the copper surface almost is not corroded.The glossiness on the surface that obtains is shown in Table 1.
Comparative example 2
Identical with embodiment 1, modulation etching reagent, and corrosion copper surface.The glossiness on the surface that obtains is shown in Table 1.
[table 1]
| Embodiment number | Form (weight %) | Glossiness |
| 1 | Diethanolamine 10 clorox 10 ammonium sulfate 6 1-vinyl imidazoles 0.8 ion exchanged water 73.2 | 82.0 |
| 2 | Monoethanolamine MEA BASF 6 clorox 10 ammonium sulfate 5 1-vinyl imidazoles 0.8 ion exchanged water 78.2 | 76.5 |
| 3 | Diethanolamine 10 clorox 10 ammonium citrates 6 1-vinyl imidazoles 0.6 ion exchanged water 73.4 | 91.3 |
| 4 | Diethanolamine 10 clorox 10 ammonium sulfate 5 benzoglyoxalines 1 ion exchanged water 74 | 83.4 |
| 5 | Monoethanolamine MEA BASF 15 sodium chlorate 15 ammonium chlorides 4 benzoglyoxalines 1 ion exchanged water 65 | 89.6 |
| 6 | Monoethanolamine MEA BASF 10 sodium chlorate 15 ammonium sulfate 5 5-methyl isophthalic acid H-tetrazoliums 1.2 ion exchanged waters 68.8 | 87.9 |
| Comparative example 1 | Diethanolamine 10 clorox 10 1-vinyl imidazoles 0.8 ion exchanged water 79.2 | 24.4 |
| Comparative example 2 | Diethanolamine 10 clorox 10 ammonium sulfate 6 ion exchanged waters 74 | 6.3 |
As shown in table 1, the etching reagent of the application of the invention can be the level and smooth surface with the glossiness more than 76.6 with the copper surface corrosion.
The present invention can provide a kind of caustic solution that makes the etching reagent of copper surface smoothing and make above-mentioned surface smoothing under the condition of gentleness.
Claims (2)
1. the etching reagent of copper or copper alloy, it is characterized in that: by the Monoethanolamine MEA BASF that is selected from that contains 1～40 weight %, the N-Mono Methyl Ethanol Amine, the N-ehtylethanolamine, the N-butylethanolamine, N, the N-dimethylethanolamine, N, the N-diethylethanolamine, 2-(2-hydroxyl) ethoxy ethanol amine, diethanolamine, N methyldiethanol amine, N butyl diethanol amine, trolamine, Propanolamine, at least a in alkanolamine that Yi Bingchunan and hydroxyethyl piperazine are formed and the ammonia soln, 1～15 weight % oxygenant, the aqueous solution of 1～10 weight % ammonium salt and 0.1～2 weight % azole compounds is formed; Described oxygenant is to be selected from least a in chloric acid, oxymuriate, chlorous acid, chlorite, hypochlorous acid and the hypochlorite.
2. the caustic solution of copper or copper alloy, it is characterized in that: make the Monoethanolamine MEA BASF that is selected from that contains 1～40 weight %, the N-Mono Methyl Ethanol Amine, the N-ehtylethanolamine, the N-butylethanolamine, N, the N-dimethylethanolamine, N, the N-diethylethanolamine, 2-(2-hydroxyl) ethoxy ethanol amine, diethanolamine, N methyldiethanol amine, N butyl diethanol amine, trolamine, Propanolamine, at least a in alkanolamine that Yi Bingchunan and hydroxyethyl piperazine are formed and the ammonia soln, 1～15 weight % oxygenant, the aqueous solution of 1～10 weight % ammonium salt and 0.1～2 weight % azole compounds contacts with the surface of copper or copper alloy, and makes described surface smoothing; Described oxygenant is to be selected from least a in chloric acid, oxymuriate, chlorous acid, chlorite, hypochlorous acid and the hypochlorite.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001169718 | 2001-06-05 | ||
| JP2001169718A JP4706081B2 (en) | 2001-06-05 | 2001-06-05 | Etching agent and etching method for copper or copper alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1389596A CN1389596A (en) | 2003-01-08 |
| CN1324164C true CN1324164C (en) | 2007-07-04 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021222509A Expired - Fee Related CN1324164C (en) | 2001-06-05 | 2002-06-03 | Copper or copper alloy corrodent and corrosion method |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4706081B2 (en) |
| CN (1) | CN1324164C (en) |
| TW (1) | TWI242608B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101337263B1 (en) * | 2004-08-25 | 2013-12-05 | 동우 화인켐 주식회사 | Etchant composition for indium oxide layer and etching method using the same |
| JP4822519B2 (en) * | 2006-06-26 | 2011-11-24 | Ｊｘ日鉱日石金属株式会社 | Semiconductor wafer pretreatment agent and pretreatment method |
| US20080224092A1 (en) * | 2007-03-15 | 2008-09-18 | Samsung Electronics Co., Ltd. | Etchant for metal |
| JP5219304B2 (en) | 2010-12-14 | 2013-06-26 | メック株式会社 | Etching agent and etching method using the same |
| JP5885971B2 (en) * | 2011-09-08 | 2016-03-16 | 関東化學株式会社 | Etching solution for copper and copper alloy |
| KR101461180B1 (en) | 2012-04-26 | 2014-11-18 | (주)삼성화학 | Copper Echant without Hydrogen Peroxide |
| CN103695908A (en) * | 2013-12-27 | 2014-04-02 | 东莞市广华化工有限公司 | Novel organic alkali micro-etching solution |
| CN104694909B (en) * | 2014-07-03 | 2017-01-25 | 广东丹邦科技有限公司 | Copper surface coarsening agent |
| KR102367814B1 (en) * | 2016-03-30 | 2022-02-25 | 동우 화인켐 주식회사 | Etching solution composition for molybdenum-containing layer and manufacturing method of an array substrate for liquid crystal display using the same |
| US11753733B2 (en) * | 2017-06-01 | 2023-09-12 | Mitsubishi Materials Corporation | Method for producing high-purity electrolytic copper |
| CN111485263B (en) * | 2019-01-25 | 2023-02-17 | 上海新阳半导体材料股份有限公司 | Lead frame deoxidant, preparation method and application thereof |
| JP6806405B1 (en) * | 2020-04-27 | 2021-01-06 | ナミックス株式会社 | Composite copper member |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0866373A (en) * | 1995-10-03 | 1996-03-12 | Terumo Corp | Temperature measurement instrument with pulse measurement function |
| US5630950A (en) * | 1993-07-09 | 1997-05-20 | Enthone-Omi, Inc. | Copper brightening process and bath |
| CN1209468A (en) * | 1997-07-08 | 1999-03-03 | 美克株式会社 | Micro-etching agent for copper and copper alloy |
| CN1223308A (en) * | 1997-10-20 | 1999-07-21 | 摩托罗拉公司 | Chemical mechanical polishing (CMP) slurry for copper and method of use in integrated circuit manufacture |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56102581A (en) * | 1980-01-17 | 1981-08-17 | Yamatoya Shokai:Kk | Etching solution of copper |
| JP2000282265A (en) * | 1999-03-31 | 2000-10-10 | Mec Kk | Microetching agent for copper or copper alloy and surface treating method using the same |
-
2001
- 2001-06-05 JP JP2001169718A patent/JP4706081B2/en not_active Expired - Lifetime
-
2002
- 2002-06-03 TW TW91111830A patent/TWI242608B/en not_active IP Right Cessation
- 2002-06-03 CN CNB021222509A patent/CN1324164C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5630950A (en) * | 1993-07-09 | 1997-05-20 | Enthone-Omi, Inc. | Copper brightening process and bath |
| JPH0866373A (en) * | 1995-10-03 | 1996-03-12 | Terumo Corp | Temperature measurement instrument with pulse measurement function |
| CN1209468A (en) * | 1997-07-08 | 1999-03-03 | 美克株式会社 | Micro-etching agent for copper and copper alloy |
| CN1223308A (en) * | 1997-10-20 | 1999-07-21 | 摩托罗拉公司 | Chemical mechanical polishing (CMP) slurry for copper and method of use in integrated circuit manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1389596A (en) | 2003-01-08 |
| JP2002363777A (en) | 2002-12-18 |
| TWI242608B (en) | 2005-11-01 |
| JP4706081B2 (en) | 2011-06-22 |
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