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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- 238000005530 etching Methods 0.000 title claims abstract description 150
- 229910017053 inorganic salt Inorganic materials 0.000 title claims abstract description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 20
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims abstract description 20
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims abstract description 10
- 239000001103 potassium chloride Substances 0.000 claims abstract description 10
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 10
- 239000004304 potassium nitrite Substances 0.000 claims abstract description 10
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- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical group OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
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- 229910052802 copper Inorganic materials 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
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- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
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Abstract
Description
技术领域 technical field
本发明涉及一种用于电化学蚀刻铜箔生产高精细线路的蚀刻液配方，特别涉及一种具有蚀刻速度稳定、蚀刻均匀、易再生和污染少等优点的无机盐蚀刻液，属于电子工业应用领域。 The invention relates to an etching solution formula for electrochemically etching copper foil to produce high-precision circuits, in particular to an inorganic salt etching solution having the advantages of stable etching speed, uniform etching, easy regeneration and less pollution, which belongs to the application in the electronics industry field.
背景技术 Background technique
目前所有电子仪器线路的设计与连接多是以印刷线路板为基础的，随着电子工业的科技进步，印制板向多层化、密集化的方向发展，蚀刻溶液配制方法逐步从过去的粗放型向专业化发展。蚀刻是印制线路板生产中的必要工序，覆铜板腐蚀法因其工艺成熟、精度较高，成为国内线路板生产的常用方法，但这种传统方法存在着工艺过程比较复杂，浪费大量铜材，对环境污染较大，线路板成本高等缺点。主要的蚀刻液有H2O2–H2SO4 溶液、酸性氯化铜溶液及碱性氯化铜溶液。刘文彬采用一种以混合酸、氧化剂和乙醇按一定比例在常温下配制的蚀刻液，每腐蚀一块线路板只需1 ~ 2 min，并能防止铜板的侧腐蚀。田波分析了在微带精密蚀刻过程中影响蚀刻速率变化的诸多因素，优化了酸性氯化铜蚀刻工艺。 At present, the design and connection of all electronic instrument circuits are mostly based on printed circuit boards. With the advancement of technology in the electronics industry, printed boards are developing in the direction of multi-layer and densification, and the etching solution preparation method has gradually changed from the previous extensive Type to professional development. Etching is a necessary process in the production of printed circuit boards. The copper clad laminate etching method has become a common method for domestic circuit board production due to its mature technology and high precision. However, this traditional method has a complicated process and wastes a lot of copper. , greater environmental pollution, higher circuit board costs and other disadvantages. The main etching solutions are H 2 O 2 -H 2 SO 4 solution, acid copper chloride solution and alkaline copper chloride solution. Liu Wenbin uses an etching solution prepared at room temperature with a certain proportion of mixed acid, oxidizing agent and ethanol. It only takes 1 to 2 minutes to corrode a circuit board, and can prevent the side corrosion of the copper plate. Tian Bo analyzed many factors that affect the change of etching rate in the microstrip precision etching process, and optimized the acidic copper chloride etching process.
目前电子工业中腐蚀铜箔制作印制电路板(PCB)时经常采用的方法是“三氯化铁化学腐蚀法”， 三氯化铁腐蚀液有许多缺点，如：不能应用于反镀法新工艺，三氯化铁耗量大，腐蚀液容量小，劳动条件差等。处理使用过的溶液工艺较复杂，回收铜及再生三氯化铁都需较复杂的设备和较大的投资。这在中、小厂一般是很难做到的，大大限制了其应用。 At present, the method often used in the electronics industry to corrode copper foil to make printed circuit boards (PCBs) is the "ferric chloride chemical corrosion method". Ferric chloride corrosion solution has many shortcomings, such as: it cannot be applied to the new anti-plating method Process, high consumption of ferric chloride, small capacity of corrosive liquid, poor working conditions, etc. The process of treating the used solution is more complicated, and the recovery of copper and the regeneration of ferric chloride require more complicated equipment and larger investment. This is generally difficult to achieve in medium and small factories, which greatly limits its application.
随着线路板精度的提高, 线宽越来越细, 化学蚀刻工艺的侧蚀问题也越来越突出, 蚀刻液不稳定、蚀刻废液等问题至今尚无满意的解决方法。随着微电子技术的迅猛发展，大规模集成电路和超大规模集成电路的广泛应用, PCB的制造技术正向着高精度的方向发展，对蚀刻技术提出了更高更严的技术要求。当导线宽度大约≤75mm时，传统的三氯化铁化学蚀刻法已不能满足高精度的需求。因此很有必要在现有技术的基础之上，研发一种蚀刻速度稳定、蚀刻均匀用于电化学蚀刻高精细线路的蚀刻液。 With the improvement of the precision of the circuit board, the line width is getting thinner and thinner, and the side erosion problem of the chemical etching process is becoming more and more prominent. There are still no satisfactory solutions to the problems of unstable etching solution and waste etching solution. With the rapid development of microelectronics technology and the wide application of large-scale integrated circuits and ultra-large-scale integrated circuits, the manufacturing technology of PCB is developing in the direction of high precision, which puts forward higher and stricter technical requirements for etching technology. When the wire width is about ≤75mm, the traditional ferric chloride chemical etching method can no longer meet the high-precision requirements. Therefore, it is necessary to develop an etching solution with stable etching speed and uniform etching for electrochemical etching of high-precision circuits on the basis of existing technologies.
发明内容 Contents of the invention
发明目的：本发明的目的是针对现有技术中存在的不足，提供一种具有蚀刻精度高，蚀刻速度稳定、蚀刻均匀、易再生、污染少等优点的用于电化学蚀刻高精细线路的蚀刻液。该蚀刻液配制方法简单，生产成本低，可满足现代印制电路板设计要求。 Purpose of the invention: the purpose of the present invention is to address the deficiencies in the prior art, to provide an etching method for electrochemically etching high-precision circuits with the advantages of high etching precision, stable etching speed, uniform etching, easy regeneration, and less pollution. liquid. The preparation method of the etching solution is simple, the production cost is low, and the design requirements of modern printed circuit boards can be met.
技术方案：为了实现以上目的，本发明采取的技术方案为： Technical scheme: in order to realize above object, the technical scheme that the present invention takes is:
一种用于电化学蚀刻高精细线路的无机盐蚀刻液，它由下列物质制成：氯化钾、亚硝酸钾、磷酸钾、配位剂、添加剂和水。 An inorganic salt etching solution for electrochemical etching of high-precision circuits, which is made of the following substances: potassium chloride, potassium nitrite, potassium phosphate, complexing agent, additives and water.
作为优选方案，以上所述的无机盐蚀刻液中氯化钾的浓度为20至40 g/L、亚硝酸钾的浓度为20至40 g/L、磷酸钾的浓度为20至40 g/L、配位剂的浓度为50至100 g/L、添加剂的浓度为50至100g/L。 As a preferred version, the concentration of potassium chloride in the above-mentioned inorganic salt etching solution is 20 to 40 g/L, the concentration of potassium nitrite is 20 to 40 g/L, and the concentration of potassium phosphate is 20 to 40 g/L , The concentration of the complexing agent is 50 to 100 g/L, and the concentration of the additive is 50 to 100 g/L.
作为更优选方案，以上所述的用于电化学蚀刻高精细线路的无机盐蚀刻液，所述的无机盐蚀刻液中氯化钾的浓度为40 g/L、亚硝酸钾的浓度为40 g/L、磷酸钾的浓度为40 g/L、配位剂的浓度为100 g/L、添加剂的浓度为100g/L。 As a more preferred version, the above-mentioned inorganic salt etching solution for electrochemically etching high-precision circuits, the concentration of potassium chloride in the described inorganic salt etching solution is 40 g/L, and the concentration of potassium nitrite is 40 g /L, the concentration of potassium phosphate is 40 g/L, the concentration of complexing agent is 100 g/L, and the concentration of additive is 100 g/L.
本发明根据高精细线路的特点，通过大量实验筛选最佳的蚀刻液组成。通过检测实验结果表明，采用本发明提供的蚀刻液组成，蚀刻速度稳定、蚀刻均匀、适用于高精度线路的蚀刻，适用范围广泛。 According to the characteristics of high-precision circuits, the present invention screens the best etching solution composition through a large number of experiments. The test results show that the etching solution provided by the invention has stable etching speed, uniform etching, is suitable for etching high-precision circuits, and has a wide range of applications.
作为优选方案，以上所述的用于电化学蚀刻高精细线路的无机盐蚀刻液，所述配位剂为羟基亚乙基二膦酸（HEDP）、EDTA二钠、柠檬酸钠中的一种或几种。本发明根据高精细线路的蚀刻特点和要求，经过大量实验筛选配位剂的种类和用量，实验结果表明本发明提供的无机盐蚀刻液蚀刻稳定、可直接回收铜、产生废液量微少、生产成本低廉。 As a preferred solution, the above-mentioned inorganic salt etching solution for electrochemically etching high-precision circuits, the complexing agent is one of hydroxyethylene diphosphonic acid (HEDP), disodium EDTA, and sodium citrate or several. According to the etching characteristics and requirements of high-precision circuits, the present invention screens the types and dosages of complexing agents through a large number of experiments. The experimental results show that the inorganic salt etching solution provided by the present invention is stable in etching, can directly recover copper, produces a small amount of waste liquid, and produces low cost.
作为优选方案，以上所述的用于电化学蚀刻高精细线路的无机盐蚀刻液，所述添加剂为甲醇、乙醇、丙酮中的一种或几种。 As a preferred solution, the above-mentioned inorganic salt etching solution for electrochemically etching high-precision circuits, the additive is one or more of methanol, ethanol, and acetone.
作为优选方案，以上所述的用于电化学蚀刻高精细线路的无机盐蚀刻液，所述无机盐蚀刻液酸碱度呈中性，pH值为6~8。采用本发明提供的无机盐蚀刻液，不会腐蚀设备和阴极材料。并且本发明提供的蚀刻液配合电化学蚀刻法可将铜箔的蚀刻精度可提升至10μm以下。并且与现有技术相比，无机盐蚀刻液的生产成本低，对设备的要求少，产生的污染物少且便于回收，具有很好的使用和推广价值。 As a preferred solution, the above-mentioned inorganic salt etching solution for electrochemically etching high-precision circuits has a neutral pH and a pH value of 6-8. Adopting the inorganic salt etchant provided by the invention will not corrode equipment and cathode materials. Moreover, the etching solution provided by the present invention cooperates with the electrochemical etching method to improve the etching precision of the copper foil to below 10 μm. And compared with the prior art, the production cost of the inorganic salt etching solution is low, the requirements for equipment are less, the pollutants produced are less and easy to recycle, and have good use and popularization value.
本发明提供的无机盐蚀刻液的配制方法是将各组分按比例加于水中，搅拌均匀至各组分完全溶于水，配制得到无色澄清的蚀刻液。 The preparation method of the inorganic salt etching solution provided by the invention is to add each component into water in proportion, stir evenly until each component is completely dissolved in water, and prepare a colorless and clear etching solution.
本发明提供的无机盐蚀刻液的使用方法是在通电下，以印制电路板为阳极，产物Cu2+溶解于电解液中, 铜离子自溶液中还原沉积在以铜片、不锈钢片或石墨片为材质的阴极的表面。 The using method of the inorganic salt etching solution provided by the present invention is under electrification, with the printed circuit board as the anode, the product Cu 2+ is dissolved in the electrolytic solution, and the copper ion is reduced and deposited on the copper sheet, stainless steel sheet or graphite from the solution. The sheet is the surface of the cathode material.
本发明提供的无机盐蚀刻液在蚀刻过程中不会产生大量的固体废弃物，通过简单的化学沉淀法即可除去蚀刻废液中过量的铜，滤液补充成分后可重复循环使用，与现有技术相比，蚀刻液易再生、污染少，可适用不断发展印制电路板发展。 The inorganic salt etching solution provided by the present invention will not produce a large amount of solid waste in the etching process, and the excessive copper in the etching waste solution can be removed by a simple chemical precipitation method, and the filtrate can be reused after replenishing components, which is different from the existing Compared with advanced technology, the etchant is easy to regenerate and has less pollution, which is suitable for the continuous development of printed circuit boards.
本发明提供的无机盐蚀刻液可与电化学方法相结合，通过控制外接电位值等条件来调节铜箔的蚀刻速度，通过控制蚀刻电路的开闭合来控制蚀刻进行的开始和结束。电化学蚀刻是将线路板作阳极产生可控制的电化学腐蚀。电化学蚀刻中阳极溶解具有方向性, 这与化学蚀刻有着本质的不同。当正面应蚀刻部位的铜箔电化学溶解完毕后, 蚀刻则不能继续进行, 线路侧面裸露的铜箔由于其方向是侧对阴极, 产生强大的电化学阻力, 侧腐蚀进行得极其缓慢。在化学蚀刻中, 蚀刻量与蚀刻时间直接正比, 强大的机械冲涮和化学腐蚀造成蚀刻没有方向性, 对线路板上线条有疏密不均匀时, 侧腐蚀是难免的。并且本发明采用电化学蚀刻还解决了整个蚀刻系统的循环问题, 由于电化学蚀刻原理是阳极Cu的氧化溶解, 阴极Cu2+的还原沉积, 即溶解在电解液中的铜离子可同时在阴极上实现电化学沉积, 既达到回收铜的目的, 又使电解液保持相对稳定的最佳组成, 整个蚀刻系统稳定、维护容易。而化学蚀刻则是靠不断向腐蚀液中加入盐酸( 酸性) 或是氨水( 碱性) 来维持蚀刻的稳定, 不仅极不方便, 而且蚀刻液会越来越多, 造成废液大量产生, 其再生处理和污染严重。因此, 采用本发明优选得到无机盐蚀刻液与电化学方法相结合，具有蚀刻液稳定、方便回收、产生的废液量少、生产成本低廉等优点。 The inorganic salt etchant provided by the invention can be combined with an electrochemical method to adjust the etching speed of copper foil by controlling the external potential value and other conditions, and to control the start and end of etching by controlling the opening and closing of the etching circuit. Electrochemical etching is to use the circuit board as an anode to produce controllable electrochemical corrosion. The anodic dissolution in electrochemical etching is directional, which is fundamentally different from chemical etching. After the electrochemical dissolution of the copper foil on the front side that should be etched is completed, the etching cannot continue. The exposed copper foil on the side of the line is oriented side-to-side to the cathode, which produces strong electrochemical resistance, and the side corrosion proceeds extremely slowly. In chemical etching, the amount of etching is directly proportional to the etching time. Strong mechanical flushing and chemical etching cause etching to have no directionality. When the lines on the circuit board are uneven, side corrosion is inevitable. And the present invention adopts electrochemical etching to also solve the cycle problem of the whole etching system, because the principle of electrochemical etching is the oxidative dissolution of anode Cu and the reductive deposition of cathode Cu 2+ , that is, the copper ions dissolved in the electrolyte can be simultaneously Electrochemical deposition is realized on the surface, which not only achieves the purpose of copper recovery, but also maintains a relatively stable optimum composition of the electrolyte. The entire etching system is stable and easy to maintain. However, chemical etching relies on continuously adding hydrochloric acid (acidic) or ammonia water (alkaline) to the etching solution to maintain the stability of etching. Recycling and serious pollution. Therefore, the combination of inorganic salt etching solution and electrochemical method is preferably obtained by the present invention, which has the advantages of stable etching solution, convenient recovery, less waste liquid generated, and low production cost.
有益效果：本发明提供的用于电化学蚀刻高精细线路的无机盐蚀刻液与现有技术相比具有以下优点： Beneficial effects: Compared with the prior art, the inorganic salt etching solution for electrochemically etching high-precision circuits provided by the present invention has the following advantages:
本发明所述的用于电化学蚀刻高精细线路的无机盐蚀刻液，通过大量实验筛选出无机盐蚀刻液的组成和和给组份的配比，通过实验结果表明本发明所述的无机盐蚀刻液与电化学方法相结合，具有蚀刻速度稳定、蚀刻均匀，蚀刻液易再生、污染少等优点，铜箔蚀刻精度可提升至10μm以下，可适用于高精细线路的蚀刻。且本发明提供的蚀刻液配制方法简单，生产成本低，可满足现代印制电路板设计要求，适用范围广泛。 The inorganic salt etching solution for electrochemically etching high-precision circuits of the present invention screens out the composition of the inorganic salt etching solution and the proportioning of the components through a large number of experiments, and the experimental results show that the inorganic salt of the present invention The combination of etching solution and electrochemical method has the advantages of stable etching speed, uniform etching, easy regeneration of etching solution, and less pollution. The etching accuracy of copper foil can be improved to below 10 μm, which is suitable for etching of high-precision circuits. Moreover, the etching solution provided by the invention has a simple preparation method and low production cost, can meet the design requirements of modern printed circuit boards, and has a wide range of applications.
附图说明 Description of drawings
图1 是电化学蚀刻装置的原理图。 Figure 1 is a schematic diagram of the electrochemical etching device.
图2是直线形印制电路板铜箔在本无机盐蚀刻液中电化学蚀刻后的光学显微镜图。 Fig. 2 is an optical microscope image of the copper foil of a linear printed circuit board after being electrochemically etched in the present inorganic salt etching solution.
图3是圆弧形印制电路板铜箔在本无机盐蚀刻液中电化学蚀刻后的光学显微镜图。 Fig. 3 is an optical micrograph of the arc-shaped printed circuit board copper foil electrochemically etched in the present inorganic salt etching solution.
图4是在本无机盐蚀刻液中电化学蚀刻后高精细线路的侧面金相显微图。 Fig. 4 is a side metallographic micrograph of the high-definition circuit after electrochemical etching in the present inorganic salt etching solution.
具体实施方案 specific implementation plan
下面结合附图和具体实施例，进一步阐明本发明，应理解这些实施例仅用于说明本发明而不用于限制本发明的范围，在阅读了本发明之后，本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定的范围。 Below in conjunction with accompanying drawing and specific embodiment, further illustrate the present invention, should be understood that these embodiments are only for illustrating the present invention and are not intended to limit the scope of the present invention, after having read the present invention, those skilled in the art will understand various aspects of the present invention Modifications in equivalent forms all fall within the scope defined by the appended claims of this application.
实施例1 Example 1
一种用于电化学蚀刻高精细线路的无机盐蚀刻液，其中无机盐蚀刻液中氯化钾的浓度为40 g/L、亚硝酸钾的浓度为40 g/L、磷酸钾的浓度为40 g/L、配位剂HEDP的浓度为100 g/L、甲醇浓度为100g/L。 An inorganic salt etching solution for electrochemically etching high-precision circuits, wherein the concentration of potassium chloride in the inorganic salt etching solution is 40 g/L, the concentration of potassium nitrite is 40 g/L, and the concentration of potassium phosphate is 40 g/L, the concentration of complexing agent HEDP is 100 g/L, and the concentration of methanol is 100 g/L.
如图1所示，电化学蚀刻装置由电解槽（1）、阴极（2）、电流分布导向板(3)、阳极( 即被蚀刻的线路板)(4) 、电解液循环管路及电解液循环泵等构成。蚀刻过程中阳极产物Cu2+溶解于电解液中, 在阴极铜离子自溶液中还原沉积在阴极上。电解液可始终保持稳定的最佳状态。 As shown in Figure 1, the electrochemical etching device consists of an electrolytic cell (1), a cathode (2), a current distribution guide plate (3), an anode (that is, the etched circuit board) (4), an electrolyte circulation pipeline and an electrolytic liquid circulation pump etc. During the etching process, the anode product Cu 2+ is dissolved in the electrolyte, and copper ions are reduced and deposited on the cathode from the solution at the cathode. Electrolyte can always maintain the best state of stability.
采用上述无机盐蚀刻液和电化学蚀刻装置相结合，印刷线路板铜箔为阳极，铜片为阴极，阴阳极面积比为10:1，外接电位为20V，阴阳极间距为2 cm，控温在50℃，采用喷淋的蚀刻方式进行印制电路板样品蚀刻，铜箔刻透时间与电位值呈线性关系。 The above-mentioned inorganic salt etching solution is combined with an electrochemical etching device. The copper foil of the printed circuit board is used as the anode, and the copper sheet is used as the cathode. At 50°C, the printed circuit board sample is etched by spray etching, and the copper foil engraving time has a linear relationship with the potential value.
直线形印制电路板铜箔在本无机盐蚀刻液中电化学蚀刻后的光学显微镜形貌如图2 所示。本发明提供的无机盐蚀刻液和电化学蚀刻结合，铜箔蚀刻均匀，边缘整齐，能够制作出线宽/线间(L/S)为30μm/30μm 高技术水准的精细印制电路。 The optical microscope morphology of the linear printed circuit board copper foil electrochemically etched in this inorganic salt etching solution is shown in Figure 2. The combination of inorganic salt etching solution and electrochemical etching provided by the invention can etch the copper foil evenly and the edges are neat, and can produce fine printed circuits with a line width/space (L/S) of 30 μm/30 μm and a high technical level.
实施例2 Example 2
一种用于电化学蚀刻高精细线路的无机盐蚀刻液，其中无机盐蚀刻液中氯化钾的浓度为40 g/L、亚硝酸钾的浓度为40 g/L、磷酸钾的浓度为40 g/L、配位剂EDTA二钠的浓度为100 g/L、乙醇浓度为100g/L。 An inorganic salt etching solution for electrochemically etching high-precision circuits, wherein the concentration of potassium chloride in the inorganic salt etching solution is 40 g/L, the concentration of potassium nitrite is 40 g/L, and the concentration of potassium phosphate is 40 g/L, the concentration of complexing agent disodium EDTA is 100 g/L, and the concentration of ethanol is 100 g/L.
采用上述无机盐蚀刻液和电化学蚀刻装置相结合，印刷线路板铜箔为阳极，石墨片作为阴极，阴阳极面积比为10:1，外接电位为10V，阴阳极间距为1 cm，控温在30℃，采用机械搅拌的蚀刻方式进行印制电路板样品蚀刻，铜箔刻透时间与电位值呈线性关系。 The above-mentioned inorganic salt etching solution is combined with an electrochemical etching device. The copper foil of the printed circuit board is used as the anode, and the graphite sheet is used as the cathode. At 30°C, the printed circuit board sample was etched by mechanical stirring etching, and the copper foil engraving time and potential value had a linear relationship.
在10V电位下，刻透圆弧形印制电路板所需时间为40 s，仅为化学蚀刻时间的一半，印制电路板的蚀刻效率更高。圆弧形印制电路板铜箔在本无机盐蚀刻液中电化学蚀刻后的蚀刻效果如图3所示。本发明完善了在不同直径的铜箔上进行电化学蚀刻的工艺，蚀刻后图形清晰，图像准确、完整未变形，导线宽度和间距高于设计要求的精度尺寸公差，达到30μm/30μm。 Under the potential of 10V, the time required for engraving the arc-shaped printed circuit board is 40 s, which is only half of the chemical etching time, and the etching efficiency of the printed circuit board is higher. The etching effect of the arc-shaped printed circuit board copper foil electrochemically etched in this inorganic salt etching solution is shown in Figure 3. The invention improves the process of electrochemical etching on copper foils with different diameters. After etching, the pattern is clear, the image is accurate, complete and undistorted, and the width and spacing of the wires are higher than the precision dimension tolerance required by the design, reaching 30μm/30μm.
实施例3 Example 3
一种用于电化学蚀刻的无机盐蚀刻液，其中无机盐蚀刻液中氯化钾的浓度为40 g/L、亚硝酸钾的浓度为40 g/L、磷酸钾的浓度为40 g/L、配位剂柠檬酸钠的浓度为100 g/L、丙酮浓度为100g/L。 An inorganic salt etching solution for electrochemical etching, wherein the concentration of potassium chloride in the inorganic salt etching solution is 40 g/L, the concentration of potassium nitrite is 40 g/L, and the concentration of potassium phosphate is 40 g/L , The concentration of the complexing agent sodium citrate is 100 g/L, and the concentration of acetone is 100 g/L.
采用上述无机盐蚀刻液和电化学蚀刻装置相结合，印刷线路板铜箔为阳极，不锈钢片作为阴极，阴阳极面积比为10:1，外接电位为15V，阴阳极间距为3 cm，控温10℃，采用喷淋的蚀刻方式进行印制电路板样品蚀刻，铜箔刻透时间与电位值呈线性关系。在本无机盐蚀刻液中电化学蚀刻后, 线路板外观整齐洁净, 0. 2mm的线间距清晰可见, 正面100倍金相显微镜观察可见线路线条边缘整齐( 采用与化学蚀刻同样的蚀刻保护油墨印刷工艺) , 如图4所示侧面250倍金相显微镜观察显示线条断面呈正梯形图形, 表明未产生侧腐蚀现象。而化学蚀刻结果通常线条断面呈倒梯形图形，和现有技术相比蚀刻质量更高。 The above-mentioned inorganic salt etching solution is combined with an electrochemical etching device. The copper foil of the printed circuit board is used as the anode, and the stainless steel sheet is used as the cathode. The area ratio of the cathode and the anode is 10:1. At 10°C, the printed circuit board sample is etched by spray etching, and the copper foil engraving time has a linear relationship with the potential value. After electrochemical etching in this inorganic salt etching solution, the appearance of the circuit board is neat and clean, the line spacing of 0.2mm is clearly visible, and the front 100 times metallographic microscope observation shows that the edges of the line lines are neat (printed with the same etching protection ink as chemical etching) process), as shown in Figure 4, the observation of the side surface with a 250-fold metallographic microscope shows that the line section is in a positive trapezoidal shape, indicating that no side corrosion occurs. The result of chemical etching is usually an inverted trapezoidal figure in the cross section of the line, and the etching quality is higher than that of the prior art.
实施例4 Example 4
一种用于电化学蚀刻高精细线路的无机盐蚀刻液，其中无机盐蚀刻液中氯化钾的浓度为20 g/L、亚硝酸钾的浓度为20 g/L、磷酸钾的浓度为20 g/L、配位剂柠檬酸钠的浓度为50 g/L、丙酮浓度为50g/L。 An inorganic salt etching solution for electrochemically etching high-precision circuits, wherein the concentration of potassium chloride in the inorganic salt etching solution is 20 g/L, the concentration of potassium nitrite is 20 g/L, and the concentration of potassium phosphate is 20 g/L g/L, the concentration of complexing agent sodium citrate is 50 g/L, and the concentration of acetone is 50 g/L.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。 The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.
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| CN101949014A (en) * | 2009-07-09 | 2011-01-19 | 株式会社Adeka | Etchant composition for copper-containing material and method for etching copper-containing material |
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| CN1899003A (en) * | 2004-03-03 | 2007-01-17 | 揖斐电株式会社 | Etching solution, method of etching and printed wiring board |
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