CN110952118A - Cyanide-free copper plating solution for ceramic circuit, preparation method and electroplating process - Google Patents
Cyanide-free copper plating solution for ceramic circuit, preparation method and electroplating process Download PDFInfo
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- CN110952118A CN110952118A CN201911144713.4A CN201911144713A CN110952118A CN 110952118 A CN110952118 A CN 110952118A CN 201911144713 A CN201911144713 A CN 201911144713A CN 110952118 A CN110952118 A CN 110952118A
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- copper plating
- copper
- cyanide
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
Abstract
The invention discloses a cyanide-free copper plating solution for ceramic circuits, a preparation method and an electroplating process, wherein the cyanide-free copper plating solution mainly comprises the following components: 15-20 g/L of copper chloride, 30-50 g/L of basic copper carbonate, 5-8 g/L of ethylene diamine tetramethylene sodium phosphate, 18-25 g/L of potassium sodium tartrate, 280-320 g/L of citric acid, 15-18 g/L of sodium bicarbonate, 0.02-0.03 g/L of selenium dioxide and a proper amount of potassium hydroxide. The copper plating solution is cyanide-free copper plating, is green and environment-friendly, and has low price of selected raw materials and low preparation cost; the copper plating solution is used for plating a copper plating layer on a ceramic circuit substrate, and the obtained copper plating layer is fine and uniform, low in porosity and good in binding force.
Description
Technical Field
The invention belongs to the technical field of ceramic circuit plating, and particularly relates to a cyanide-free copper plating solution for a ceramic circuit, a preparation method and an electroplating process.
Background
The ceramic circuit is an interconnection circuit structure manufactured on a ceramic substrate, has the characteristics of high interconnection density, high line precision and the like, can realize small hole metallization, is used for manufacturing passive elements such as integrated resistors, capacitors and inductors and high-power circuits, and has wide application in the fields of airborne, spaceborne, aerospace and the like. The ceramic circuit should have qualified electrical properties and also meet the technical requirements of the subsequent assembly process. The metal copper has the characteristics of low resistivity, high reliability, small size of an interconnecting wire, high density, high migration resistance and the like, has smaller resistivity than common metals of thin-film circuits such as gold, nickel and the like, has small circuit loss when being used as a main body layer of a ceramic circuit, and has lower production cost, so the copper is a very important metal in a ceramic circuit coating. The quality of the copper layer directly affects the overall performance of the circuit.
The existing copper plating process of the ceramic circuit can be divided into cyanide copper plating and cyanide-free copper plating. Cyanide copper plating has been banned because cyanide plating solutions contain cyanide and are highly toxic and cause significant environmental pollution. Cyanide-free copper plating has become more and more widely used due to its lower toxicity.
Disclosure of Invention
The invention aims to provide a cyanide-free copper plating solution for a ceramic circuit, a preparation method and an electroplating process.
The technical solution for realizing the purpose of the invention is as follows: a cyanide-free copper plating solution for ceramic circuits, which mainly comprises: 15-20 g/L of copper chloride, 30-50 g/L of basic copper carbonate, 5-8 g/L of ethylene diamine tetramethylene sodium phosphate, 18-25 g/L of potassium sodium tartrate, 280-320 g/L of citric acid, 15-18 g/L of sodium bicarbonate, 0.02-0.03 g/L of selenium dioxide and a proper amount of potassium hydroxide, wherein the potassium hydroxide is used for adjusting the pH value of the solution to enable the pH value to meet 9-10.
A preparation method of a cyanide-free copper plating solution for a ceramic circuit comprises the following preparation processes:
dissolving citric acid by using pure water, adding potassium hydroxide until the pH value of the mixed solution is between 3 and 4, and adding copper chloride and basic copper carbonate into the solution to completely dissolve the copper chloride and the basic copper carbonate;
adding potassium hydroxide to the solution under vigorous stirring;
finally, adding a mixed solution of ethylene diamine tetraacetic acid sodium phosphate, sodium bicarbonate and selenium dioxide into the solution, and stirring uniformly to complete the preparation.
A plating process based on a cyanide-free copper plating solution for ceramic circuits comprises the following steps:
oil removal: removing pollutants on the surface of the ceramic circuit;
washing with tap water: removing the residual solution in the oil removing process;
activating with hydrochloric acid: removing an oxide layer existing in the substrate material by using 50% hydrochloric acid to expose the substrate to be plated;
washing with pure water: removing the solution remained in the activation process;
pre-copper plating: plating copper by heavy current impact;
washing with pure water: removing the residual solution in the pre-plating process;
copper plating: plating a layer of copper plating layer on a ceramic circuit substrate by using a cyanide-free copper plating solution for the ceramic circuit, wherein the temperature of the solution is as follows: 35-55 ℃, pH: 9-10, current density: 0.5A/dm2～3A/dm2。
Compared with the prior art, the invention has the beneficial effects that: (1) the copper plating solution is cyanide-free copper plating, is green and environment-friendly, and has small harm to the environment; (2) the raw materials adopted by the copper plating solution formula method are low in price and the preparation cost is low; (3) the solution is static for more than 4 months without obvious precipitate, the stability of the plating solution is good, the current density range of the solution is wide, the current efficiency is high, and the solution dispersing capacity and the covering capacity are good; (4) the copper plating solution is used for plating a copper plating layer on a ceramic circuit substrate, and the obtained copper plating layer is fine and uniform, low in porosity and good in binding force.
Detailed Description
A cyanide-free copper plating solution for ceramic circuits, which mainly comprises: 15-20 g/L of copper chloride, 30-50 g/L of basic copper carbonate, 5-8 g/L of ethylene diamine tetramethylene sodium phosphate (EDTMPS), 18-25 g/L of potassium sodium tartrate, 280-320 g/L of citric acid, 15-18 g/L of sodium bicarbonate, 0.02-0.03 g/L of selenium dioxide and a proper amount of potassium hydroxide; and the potassium hydroxide is used for adjusting the pH value of the solution to enable the pH value to meet 9-10.
A method for preparing a cyanide-free copper plating solution for a ceramic circuit comprises the following preparation processes: dissolving citric acid by using a proper amount of pure water, adding slow potassium hydroxide until the pH value of the mixed solution is between 3 and 4, and adding copper chloride and basic copper carbonate into the solution to completely dissolve the copper chloride and the basic copper carbonate; adding potassium hydroxide into the solution under strong stirring, and adding mixed solution of ethylene diamine tetra methyl sodium phosphate (EDTMPS), sodium bicarbonate and selenium dioxide into the solution, and stirring well to obtain the final product. Wherein the intensive stirring is 3-5 circulation stirring per hour.
A plating process based on a cyanide-free copper plating solution for ceramic circuits comprises the following steps:
oil removal: removing pollutants on the surface of the ceramic circuit, including oil stains, fingerprints and stains;
washing with tap water: removing the residual solution in the oil removing process;
activating with hydrochloric acid: removing an oxide layer existing in the substrate material by using hydrochloric acid with the volume fraction of 50% to expose a fresh substrate to be plated;
washing with pure water: removing the solution remained in the activation process, and avoiding that chloride ions are possibly brought into the plating solution after washing with tap water;
pre-copper plating: the copper is plated by heavy current impact, so that the binding force between the substrate and a subsequent copper plating layer is improved; wherein the current density is 2A/dm2。
Washing with pure water: removing the residual solution in the pre-plating process, and avoiding that chloride ions are possibly brought into the plating solution after washing with tap water;
copper plating: plating a copper plating layer with qualified appearance and good binding force on a ceramic circuit substrate; temperature: 35-55 ℃, pH: 9-10, current density: 0.5A/dm2～3A/dm2Mainly comprises the following steps: 15-20 g/L of copper chloride, 30-50 g/L of basic copper carbonate, 5-8 g/L of ethylene diamine tetramethylene sodium phosphate (EDTMPS), 18-25 g/L of potassium sodium tartrate, 280-320 g/L of citric acid, 15-18 g/L of sodium bicarbonate, 0.02-0.03 g/L of selenium dioxide and a proper amount of potassium hydroxide.
Further, the thickness of the copper plating layer is 1-2 microns.
The present invention will be described in detail below with reference to examples.
Example 1
In the embodiment, for copper plating of an alumina ceramic circuit, the electroplating process comprises the following steps:
oil removal: removing oil stains, finger prints, stains and other pollutants on the surface of the ceramic circuit;
washing with tap water: removing the residual solution in the oil removing process;
activating with hydrochloric acid: removing an oxide layer existing in the substrate material by using 50% hydrochloric acid to expose a fresh substrate to be plated;
washing with pure water: removing the solution remained in the activation process, and avoiding that chloride ions are possibly brought into the plating solution after washing with tap water;
pre-copper plating: the copper is plated by heavy current impact, and the binding force of the substrate and a subsequent copper plating layer is improved.
Washing with pure water: removing the residual solution in the pre-plating process, and avoiding that chloride ions are possibly brought into the plating solution after washing with tap water;
copper plating: plating a copper plating layer with the thickness of 1 micron on the ceramic circuit substrate; temperature: 40 ℃, pH: 9-10, current density: 1A/dm2Mainly comprises the following steps: 15-20 g/L of copper chloride, 30-50 g/L of basic copper carbonate, 5-8 g/L of ethylene diamine tetramethylene sodium phosphate (EDTMPS), 18-25 g/L of potassium sodium tartrate, 280-320 g/L of citric acid, 15-18 g/L of sodium bicarbonate, 0.02-0.03 g/L of selenium dioxide and a proper amount of potassium hydroxide. And the potassium hydroxide is used for adjusting the pH value of the solution to enable the pH value to meet 9-10.
Example 2
In this embodiment, the copper plating and electroplating process for the aluminum nitride ceramic circuit includes the following steps:
oil removal: removing oil stains, finger prints, stains and other pollutants on the surface of the ceramic circuit;
washing with tap water: removing the residual solution in the oil removing process;
activating with hydrochloric acid: removing an oxide layer existing in the substrate material by using 50% hydrochloric acid to expose a fresh substrate to be plated;
washing with pure water: removing the solution remained in the activation process, and avoiding that chloride ions are possibly brought into the plating solution after washing with tap water;
pre-copper plating: the copper is plated by heavy current impact, and the binding force of the substrate and a subsequent copper plating layer is improved.
Washing with pure water: removing the residual solution in the pre-plating process, and avoiding that chloride ions are possibly brought into the plating solution after washing with tap water;
copper plating: plating a 1-micron copper plating layer on a ceramic circuit substrate; temperature: 35-55 ℃, pH: 9-10, current density: 0.5A/dm2～3A/dm2Mainly comprises the following steps: 15-20 g/L of copper chloride, 30-50 g/L of basic copper carbonate, 5-8 g/L of ethylene diamine tetramethylene sodium phosphate (EDTMPS), 18-25 g/L of potassium sodium tartrate, 280-320 g/L of citric acid, 15-18 g/L of sodium bicarbonate, 0.02-0.03 g/L of selenium dioxide and a proper amount of potassium hydroxide. And the potassium hydroxide is used for adjusting the pH value of the solution to enable the pH value to meet 9-10.
Example 3
In this embodiment, the copper plating and electroplating process for the printed circuit-PCB includes the following steps:
oil removal: removing oil stains, finger prints, stains and other pollutants on the surface of the ceramic circuit;
washing with tap water: removing the residual solution in the oil removing process;
activating with hydrochloric acid: removing an oxide layer existing in the substrate material by using 50% hydrochloric acid to expose a fresh substrate to be plated;
washing with pure water: removing the solution remained in the activation process, and avoiding that chloride ions are possibly brought into the plating solution after washing with tap water;
pre-copper plating: the copper is plated by heavy current impact, and the binding force of the substrate and a subsequent copper plating layer is improved.
Washing with pure water: removing the residual solution in the pre-plating process, and avoiding that chloride ions are possibly brought into the plating solution after washing with tap water;
copper plating: plating a 2-micron copper plating layer on a ceramic circuit substrate; temperature: 35-55 ℃, pH: 9-10, current density: 0.5A/dm2～3A/dm2Mainly comprises the following steps: 15-20 g/L of copper chloride, 30-50 g/L of basic copper carbonate, 5-8 g/L of ethylene diamine tetramethylene sodium phosphate (EDTMPS), 18-25 g/L of potassium sodium tartrate, 280-320 g/L of citric acid, 15-18 g/L of sodium bicarbonate, 0.02-0.03 g/L of selenium dioxide and a proper amount of potassium hydroxide. The potassium hydroxide is used for adjusting the pH value of the solution to enable the pH value to meet 9～10。
The above are only preferred embodiments of the present invention, and should not be limited by the scope of the present invention, and all the equivalent changes and modifications made by the claims and the content of the specification of the present invention should be covered by the scope of the present invention.
Claims (6)
1. A cyanide-free copper plating solution for ceramic circuits, which is characterized by mainly comprising: 15-20 g/L of copper chloride, 30-50 g/L of basic copper carbonate, 5-8 g/L of ethylene diamine tetramethylene sodium phosphate, 18-25 g/L of potassium sodium tartrate, 280-320 g/L of citric acid, 15-18 g/L of sodium bicarbonate, 0.02-0.03 g/L of selenium dioxide and a proper amount of potassium hydroxide, wherein the potassium hydroxide is used for adjusting the pH value of the solution to enable the pH value to meet 9-10.
2. A method of preparing the cyanide-free copper plating solution for ceramic circuits of claim 1, wherein the preparation process comprises:
dissolving citric acid by using pure water, adding potassium hydroxide until the pH value of the mixed solution is between 3 and 4, and adding copper chloride and basic copper carbonate into the solution to completely dissolve the copper chloride and the basic copper carbonate;
adding potassium hydroxide to the solution under vigorous stirring;
finally, adding a mixed solution of ethylene diamine tetraacetic acid sodium phosphate, sodium bicarbonate and selenium dioxide into the solution, and stirring uniformly to complete the preparation.
3. The method for preparing a cyanide-free copper plating solution for ceramic circuits according to claim 2, wherein potassium hydroxide is added to the solution under vigorous stirring, and the temperature of the mixed solution during the addition process does not exceed 50 ℃.
4. A plating process based on the cyanide-free copper plating solution for ceramic circuits of claim 1, comprising the steps of:
oil removal: removing pollutants on the surface of the ceramic circuit;
washing with tap water: removing the residual solution in the oil removing process;
activating with hydrochloric acid: removing an oxide layer existing in the substrate material by using 50% hydrochloric acid to expose the substrate to be plated;
washing with pure water: removing the solution remained in the activation process;
pre-copper plating: plating copper by heavy current impact;
washing with pure water: removing the residual solution in the pre-plating process;
copper plating: plating a layer of copper plating layer on a ceramic circuit substrate by using a cyanide-free copper plating solution for a ceramic circuit, wherein the plating temperature is 35-55 ℃, the pH is 9-10, and the current density is 0.5A/dm2～3A/dm2。
5. The process of claim 4, wherein the ceramic circuit cyanide-free copper plating solution is used to deposit a copper layer on the ceramic circuit substrate to a thickness of 1 to 2 microns.
6. The process of claim 4, wherein the pre-copper plating process has a current density of 2A/dm2。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911144713.4A CN110952118A (en) | 2019-11-20 | 2019-11-20 | Cyanide-free copper plating solution for ceramic circuit, preparation method and electroplating process |
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| CN201911144713.4A CN110952118A (en) | 2019-11-20 | 2019-11-20 | Cyanide-free copper plating solution for ceramic circuit, preparation method and electroplating process |
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| CN102549196A (en) * | 2009-09-28 | 2012-07-04 | 安美特德国有限公司 | Process for applying a metal coating to a non-conductive substrate |
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| CN105624749A (en) * | 2016-03-28 | 2016-06-01 | 上海申和热磁电子有限公司 | Method for surface metallization of ceramic substrate |
| CN106498454A (en) * | 2016-10-14 | 2017-03-15 | 吴迪 | A kind of preparation method of biomass cyanideless electro-plating liquid |
| CN107708315A (en) * | 2017-10-31 | 2018-02-16 | 江苏贺鸿电子有限公司 | A kind of ceramic embedded radiating circuit plate and preparation method thereof |
| CN107771227A (en) * | 2015-04-20 | 2018-03-06 | 埃托特克德国有限公司 | Electrolytic copper plating bath composition and usage thereof |
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2019
- 2019-11-20 CN CN201911144713.4A patent/CN110952118A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1565149A (en) * | 2001-10-04 | 2005-01-12 | 奥克-三井有限公司 | Nickel coated copper as electrodes for embedded passive devices |
| CN1910041A (en) * | 2004-01-13 | 2007-02-07 | 宇部兴产株式会社 | Polyimide metal laminate and circuit substrate |
| JP2009024203A (en) * | 2007-07-18 | 2009-02-05 | Okuno Chem Ind Co Ltd | Electrolytic copper plating |
| CN101550569A (en) * | 2009-04-13 | 2009-10-07 | 昆明理工大学 | Non-cyanide alkaline copper plating bath, preparation and use method thereof |
| CN102549196A (en) * | 2009-09-28 | 2012-07-04 | 安美特德国有限公司 | Process for applying a metal coating to a non-conductive substrate |
| CN105189827A (en) * | 2013-05-13 | 2015-12-23 | 埃托特克德国有限公司 | Method for depositing thick copper layers onto sintered materials |
| CN107771227A (en) * | 2015-04-20 | 2018-03-06 | 埃托特克德国有限公司 | Electrolytic copper plating bath composition and usage thereof |
| CN105624749A (en) * | 2016-03-28 | 2016-06-01 | 上海申和热磁电子有限公司 | Method for surface metallization of ceramic substrate |
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Application publication date: 20200403 |