CN102691063B - Inorganic salt etching solution used for electrochemically etching highly fine lines - Google Patents
Inorganic salt etching solution used for electrochemically etching highly fine lines Download PDFInfo
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- CN102691063B CN102691063B CN2012101940585A CN201210194058A CN102691063B CN 102691063 B CN102691063 B CN 102691063B CN 2012101940585 A CN2012101940585 A CN 2012101940585A CN 201210194058 A CN201210194058 A CN 201210194058A CN 102691063 B CN102691063 B CN 102691063B
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Abstract
The invention discloses an inorganic salt etching solution used for electrochemically etching highly fine lines. The inorganic salt etching solution is prepared from the following gcomponents: potassium chloride, potassium nitrite, potassium phosphate, coordination agent, additive and water. The concentration of each component of the inorganic salt etching solution is accurate, the accuracy of the copper foil of a printed-circuit board can be controlled below 10 mum by an electrochemically etching method, the etching accuracy is high, the etching speed is stable, the etching is uniform, the etching solution is easy to regenerate and has small pollution, a preparation method of the inorganic salt etching solution is simple, and the inorganic salt etching solution has low production cost, a wide application scope and good economic and social benefits.
Description
Technical field
The present invention relates to a kind of etching solution formula of producing the fine circuit for the chemical etching Copper Foil, particularly a kind of have an inorganic salt etching solution that etching speed is stable, etching evenly, is easily regenerated and pollutes advantages such as lacking, belongs to the Application to Electronic Industry field.
Background technology
Mostly the at present design of all electronic machine circuits is take printed-wiring board (PWB) as basic with being connected, scientific-technical progress along with electronic industry, printed board is to the future development of multiple stratification, densification, and the etching solution compound method is progressively from the extensive style in past to professional development.Etching is the necessary operation during printed circuit board is produced, the copper-clad plate etch is higher because of its technical maturity, precision, become the common method that the national line plate is produced, but this traditional method exists the technological process more complicated, waste a large amount of copper materials, environmental pollution is larger, wiring board high in cost of production shortcoming.Main etching solution has H
2O
2– H
2SO
4Solution, acid chlorization copper solutions and alkaline Cupric Chloride Solution.Liu Wenbin adopts a kind of etching solution of preparing at normal temperatures by a certain percentage with mixing acid, oxygenant and ethanol, and wiring board of every corrosion only needs 1 ~ 2 min, and can prevent the side corrosion of copper coin.The field wave analysis at little factors that affects change in etch rate in the fine etching process, optimized the acidic copper chloride etch process.
The method that often adopts when in electronic industry, the corrosion Copper Foil is made printed circuit board (PCB) at present is " iron trichloride chemical corrosion method ", the iron trichloride corrosive fluid has many shortcomings, as: can not be applied to the anti-method novel process of plating, the iron trichloride consumption is large, the corrosive fluid capacity is little, and labor condition is poor etc.Process used solution process more complicated, recovery copper and regeneration iron trichloride all need more complicated equipment and larger investment.This generally is difficult to accomplish in middle or small factory, has greatly limited its application.
Along with the raising of wiring board precision, live width is more and more thinner, and the lateral erosion problem of chemical etching process is also more and more outstanding, and the problems such as etching solution is unstable, etching waste liquor there is no satisfied solution so far.Along with the fast development of microelectronics, the widespread use of large-scale integrated circuit and super large-scale integration, the manufacturing technology of PCB, just towards high-precision future development, has proposed the more technical requirements of Gao Gengyan to etching technique.When conductor width approximately≤during 75mm, traditional iron trichloride chemical method for etching can not meet high-precision demand.Therefore necessary on the basis of prior art, research and develop that a kind of etching speed is stable, etching is evenly for the etching solution of chemical etching fine circuit.
Summary of the invention
Goal of the invention: the objective of the invention is for the deficiencies in the prior art, provide that a kind of to have the etching precision high, etching speed is stable, etching evenly, easily regeneration, pollute the etching solution that is used for chemical etching fine circuit of the advantage such as few.This etching solution compound method is simple, and production cost is low, can meet modern Printed Circuit Board Design requirement.
Technical scheme: in order to realize above purpose, the technical scheme that the present invention takes is:
A kind of inorganic salt etching solution for chemical etching fine circuit, it is made by following material: Repone K, potassium nitrite, potassiumphosphate, coordination agent, additive and water.
As preferred version, in above-described inorganic salt etching solution, the concentration of Repone K is that the concentration of 20 to 40 g/L, potassium nitrite is that the concentration of 20 to 40 g/L, potassiumphosphate is that the concentration of 20 to 40 g/L, coordination agent is that the concentration of 50 to 100 g/L, additive is 50 to 100g/L.
As more preferably scheme, above-described inorganic salt etching solution for chemical etching fine circuit, in described inorganic salt etching solution, the concentration of Repone K is that the concentration of 40 g/L, potassium nitrite is that the concentration of 40 g/L, potassiumphosphate is that the concentration of 40 g/L, coordination agent is that the concentration of 100 g/L, additive is 100g/L.
The present invention, according to the characteristics of fine circuit, screens best etching solution by great many of experiments and forms.Show by the test experience result, adopt etching solution provided by the invention to form, the etching that etching speed is stable, etching is even, be applicable to the high precision circuit, applied widely.
As preferred version, above-described inorganic salt etching solution for chemical etching fine circuit, described coordination agent are one or more in hydroxy ethylene diphosphonic acid (HEDP), EDETATE SODIUM, Trisodium Citrate.The present invention is according to the etching Liquified gas tanker of fine circuit, through kind and the consumption of great many of experiments screening coordination agent, experimental result shows that inorganic salt etching solution provided by the invention etching is stable, can directly reclaim copper, produces waste liquid amount pettiness, low production cost.
As preferred version, above-described inorganic salt etching solution for chemical etching fine circuit, described additive is one or more in methyl alcohol, ethanol, acetone.
As preferred version, above-described inorganic salt etching solution for chemical etching fine circuit, it is neutral that described inorganic salt etching solution potential of hydrogen is, and the pH value is 6 ~ 8.Adopt inorganic salt etching solution provided by the invention, can etching apparatus and cathode material.And etching solution provided by the invention coordinates the chemical etching method etching precision of Copper Foil can be able to be promoted to below 10 μ m.And compared with prior art, the production cost of inorganic salt etching solution is low, and is few to the requirement of equipment, and the pollutent of generation is few and be convenient to recovery, has good value for applications.
The compound method of inorganic salt etching solution provided by the invention is that each component is added in water in proportion, stirs fully water-soluble to each component, and preparation obtains the etching solution of achromaticity and clarification.
The using method of inorganic salt etching solution provided by the invention is under energising, take printed circuit board as anode, and product C u
2+Be dissolved in electrolytic solution, cupric ion in solution reduce deposition on the surface of the negative electrode take copper sheet, stainless steel substrates or graphite flake as material.
Inorganic salt etching solution provided by the invention can not produce a large amount of solid waste in etching process, can remove copper excessive in etching waste liquor by simple chemical precipitation method, after the filtrate complementary element, but recirculation is used, compared with prior art, etching solution easily regenerates, pollutes few, applicable development printed circuit board development.
Inorganic salt etching solution provided by the invention can combine with electrochemical method, regulates the etching speed of Copper Foil by controlling the conditions such as external potential value, beginning and the end undertaken by the incompatible control etching of switching of controlling etched circuit.Chemical etching is wiring board to be made anode produce controllable galvanic corrosion.The chemical etching Anodic dissolves and has directivity, and this and chemical milling are essentially different.After front answered the Copper Foil electrochemical dissolution at etching position complete, etching can not be proceeded, and the exposed Copper Foil in circuit side, because its direction is the side anticathode, produces powerful electrochemistry resistance, and the side corrosion is carried out extremely slowly.In chemical milling, the direct direct ratio of etch quantity and etching period, powerful machinery are washed away with chemical corrosion and are caused etching there is no directivity, and while to lines on wiring board, having density inhomogeneous, the side corrosion is unavoidable.And the present invention adopts chemical etching also to solve the circulatory problems of whole etch system, is the oxidation dissolution of positive C u due to the chemical etching principle, negative electrode Cu
2+Reduce deposition, the cupric ion that namely is dissolved in electrolytic solution can simultaneously be realized electrochemical deposition on negative electrode, both reached the purpose that reclaims copper, and the best that electrolytic solution keeps relative stability is formed, whole etch system is stable, safeguard easily.Chemical milling is by constantly adding hydrochloric acid (acidity) or ammoniacal liquor (alkalescence) to keep etched stablizing in corrosive fluid, not only extremely inconvenient, and etching solution can get more and more, and causes waste liquid to produce in a large number, its manipulation of regeneration and seriously polluted.Therefore, adopt the present invention preferably to obtain the inorganic salt etching solution and combine with electrochemical method, have the advantages such as stable, the convenient waste liquid amount that reclaims, produces of etching solution is few, low production cost.
Beneficial effect: the inorganic salt etching solution for chemical etching fine circuit provided by the invention compared with prior art has the following advantages:
Inorganic salt etching solution for chemical etching fine circuit of the present invention, by great many of experiments filter out the inorganic salt etching solution composition and and the proportioning of giving component, result shows that inorganic salt etching solution of the present invention combines with electrochemical method by experiment, have that etching speed is stable, etching is even, the advantages such as few are easily regenerated, polluted to etching solution, Copper Foil etching precision can be promoted to below 10 μ m, applicable to the etching of fine circuit.And etching solution compound method provided by the invention is simple, and production cost is low, can meet modern Printed Circuit Board Design requirement, and is applied widely.
Description of drawings
Fig. 1 is the schematic diagram of chemical etching device.
Fig. 2 is linear printed circuit board Copper Foil opticmicroscope figure after chemical etching in these inorganic salt etching solution.
Fig. 3 is circular arc printed circuit board Copper Foil opticmicroscope figure after chemical etching in these inorganic salt etching solution.
Fig. 4 is the side metallurgical microscopic of fine circuit after chemical etching in these inorganic salt etching solution.
Specific embodiments
Below in conjunction with the drawings and specific embodiments, further illustrate the present invention, should understand these embodiment only is not used in and limits the scope of the invention for explanation the present invention, after having read the present invention, those skilled in the art all fall within the application's claims limited range to the modification of the various equivalent form of values of the present invention.
A kind of inorganic salt etching solution for chemical etching fine circuit, wherein in the inorganic salt etching solution, the concentration of Repone K is that the concentration of 40 g/L, potassium nitrite is that the concentration of 40 g/L, potassiumphosphate is that the concentration of 40 g/L, coordination agent HEDP is that 100 g/L, methanol concentration are 100g/L.
As shown in Figure 1, the chemical etching device is by formations such as electrolyzer (1), negative electrode (2), distribution of current guide plate (3), anode (being etched wiring board) (4), circulation of elecrolyte pipeline and electrolyte circulating pumps.Etching process Anodic product C u
2+Be dissolved in electrolytic solution, the cathode copper ion in solution reduce deposition on negative electrode.Electrolytic solution can remain stable optimum regime.
Adopt above-mentioned inorganic salt etching solution and chemical etching device to combine, the printed-wiring board (PWB) Copper Foil is anode, copper sheet is negative electrode, ratio of cathodic to anodic area is 10:1, external current potential is 20V, and cathode and anode spacing is 2 cm, and temperature control is at 50 ℃, adopt the etching mode of spray to carry out the etching of printed circuit board sample, Copper Foil saturating time at quarter and potential value are linear.
Linear printed circuit board Copper Foil in these inorganic salt etching solution the opticmicroscope pattern after chemical etching as shown in Fig. 2.Inorganic salt etching solution provided by the invention and chemical etching combination, the Copper Foil etching is even, neat in edge, can produce (L/S) between live width/line is the meticulous printed electronic circuit of 30 μ m/30 μ m hi-tech levels.
A kind of inorganic salt etching solution for chemical etching fine circuit, wherein in the inorganic salt etching solution, the concentration of Repone K is that the concentration of 40 g/L, potassium nitrite is that the concentration of 40 g/L, potassiumphosphate is that the concentration of 40 g/L, coordination agent EDETATE SODIUM is that 100 g/L, alcohol concn are 100g/L.
Adopt above-mentioned inorganic salt etching solution and chemical etching device to combine, the printed-wiring board (PWB) Copper Foil is anode, graphite flake is as negative electrode, ratio of cathodic to anodic area is 10:1, external current potential is 10V, and cathode and anode spacing is 1 cm, and temperature control is at 30 ℃, adopt churned mechanically etching mode to carry out the etching of printed circuit board sample, Copper Foil saturating time at quarter and potential value are linear.
Under the 10V current potential, carving saturating circular arc printed circuit board required time is 40 s, is only half of chemical milling time, and the etching efficiency of printed circuit board is higher.The etch effect after chemical etching is as shown in Figure 3 in these inorganic salt etching solution for circular arc printed circuit board Copper Foil.The present invention is perfect carries out the technique of chemical etching on the Copper Foil of different diameter, after etching, figure is clear, accurate, the complete not distortion of image, and conductor width and spacing, higher than the precision tolerance of dimension of design requirements, reach 30 μ m/30 μ m.
A kind of etching solution of inorganic salt for chemical etching, wherein in the inorganic salt etching solution, the concentration of Repone K is that the concentration of 40 g/L, potassium nitrite is that the concentration of 40 g/L, potassiumphosphate is that the concentration of 40 g/L, coordination agent Trisodium Citrate is that 100 g/L, acetone concentration are 100g/L.
Adopt above-mentioned inorganic salt etching solution and chemical etching device to combine, the printed-wiring board (PWB) Copper Foil is anode, stainless steel substrates is as negative electrode, ratio of cathodic to anodic area is 10:1, external current potential is 15V, and cathode and anode spacing is 3 cm, 10 ℃ of temperature controls, adopt the etching mode of spray to carry out the etching of printed circuit board sample, Copper Foil saturating time at quarter and potential value are linear.In these inorganic salt etching solution after chemical etching; the wiring board outward appearance is neatly clean; 0. the distance between centers of tracks of 2mm is high-visible; positive 100 times of metallography microscope sem observation object line route bar neat in edge (adopting the etching protection printing ink printing art same with chemical milling); 250 times of sides metallography microscope sem observation display line bar section is the trapezoid figure as shown in Figure 4, shows and does not produce the side corrosion phenomenon.And the common lines section of chemical milling result is the inverted trapezoidal figure, and compared to the prior art etching quality is higher.
A kind of inorganic salt etching solution for chemical etching fine circuit, wherein in the inorganic salt etching solution, the concentration of Repone K is that the concentration of 20 g/L, potassium nitrite is that the concentration of 20 g/L, potassiumphosphate is that the concentration of 20 g/L, coordination agent Trisodium Citrate is that 50 g/L, acetone concentration are 50g/L.
The above is only the preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (3)
1. inorganic salt etching solution that is used for chemical etching fine circuit, it is characterized in that: it is made by following material: Repone K, potassium nitrite, potassiumphosphate, coordination agent, additive and water;
In described inorganic salt etching solution, the concentration of Repone K is that the concentration of 40g/L, potassium nitrite is that the concentration of 40g/L, potassiumphosphate is that the concentration of 40g/L, coordination agent is that the concentration of 100g/L, additive is 100g/L;
Described coordination agent is hydroxy ethylene diphosphonic acid or Trisodium Citrate;
Described additive is acetone;
It is neutral that described inorganic salt etching solution potential of hydrogen is, and the pH value is 6～8.
2. one kind is carried out the chemical etching Copper Foil with the inorganic salt etching solution for chemical etching fine circuit claimed in claim 1 and produces the method for fine circuit, it is characterized in that: described inorganic salt etching solution combines with electrochemical method, regulate the etching speed of Copper Foil by controlling external potential value, beginning and the end undertaken by the incompatible control etching of switching of controlling etched circuit.
3. the inorganic salt etching solution for chemical etching fine circuit according to claim 1, it is characterized in that: Copper Foil etching precision is below 10 μ m.
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| CN106400098A (en) * | 2016-05-26 | 2017-02-15 | 区佩金 | Novel etching solution and process thereof |
| CN107587135A (en) * | 2016-07-08 | 2018-01-16 | 深圳新宙邦科技股份有限公司 | A kind of molybdenum aluminium-molybdenum etching liquid |
| CN108668452A (en) * | 2018-06-12 | 2018-10-16 | 江苏博敏电子有限公司 | A kind of PCB fine-lines electrolytic etching recycles correlation technology with copper |
| CN109640537B (en) * | 2019-01-31 | 2021-05-28 | 生益电子股份有限公司 | PCB film removing device for preventing PCB from being oxidized under alkaline condition |
| CN115985882A (en) * | 2023-02-15 | 2023-04-18 | 江苏富乐华半导体科技股份有限公司 | Graphic layer structure of thick aluminum ceramic lining plate and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4632727A (en) * | 1985-08-12 | 1986-12-30 | Psi Star | Copper etching process and solution |
| CN1899003A (en) * | 2004-03-03 | 2007-01-17 | 揖斐电株式会社 | Etching solution, method of etching and printed wiring board |
| CN101180419A (en) * | 2004-12-06 | 2008-05-14 | 皇家飞利浦电子股份有限公司 | Etchant solutions and additives therefor |
| CN101949014A (en) * | 2009-07-09 | 2011-01-19 | 株式会社Adeka | Etchant composition for and etching method of materials containing copper |
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2012
- 2012-06-13 CN CN2012101940585A patent/CN102691063B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4632727A (en) * | 1985-08-12 | 1986-12-30 | Psi Star | Copper etching process and solution |
| CN1899003A (en) * | 2004-03-03 | 2007-01-17 | 揖斐电株式会社 | Etching solution, method of etching and printed wiring board |
| CN101180419A (en) * | 2004-12-06 | 2008-05-14 | 皇家飞利浦电子股份有限公司 | Etchant solutions and additives therefor |
| CN101949014A (en) * | 2009-07-09 | 2011-01-19 | 株式会社Adeka | Etchant composition for and etching method of materials containing copper |
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