阅读说明：本技术 一种厚钼板的蚀刻液及其制备方法 (Etching solution for thick molybdenum plate and preparation method thereof ) 是由 王康 赵振刚 任柴 于 2020-06-22 设计创作，主要内容包括：本申请提供了一种厚钼板的蚀刻液及其制备方法,涉及钼板蚀刻技术领域,以体积计量,含有10％～15％的H<Sub>2</Sub>SO<Sub>4</Sub>、20％～35％的HNO<Sub>3</Sub>和5％～10％的含醚键有机添加剂,余量为H<Sub>2</Sub>O；在蚀刻厚钼板时,能够保证蚀刻底纹均匀、侧蚀小；能够保证钼蚀刻制品有较好的尺寸精度和尺寸均匀性；并且能够适用于实际生产中进行批量化生产。(The application provides an etching solution for a thick molybdenum plate and a preparation method thereof, which relate to the technical field of molybdenum plate etching and comprise 10-15% of H by volume 2 SO 4 20 to 35 percent of HNO 3 And 5-10% of organic additive containing ether bond, and the balance of H 2 O; when the thick molybdenum plate is etched, the uniform etching bottom pattern and small side etching can be ensured; the method can ensure that the molybdenum etching product has better dimensional accuracy and dimensional uniformity; and can be suitable for batch production in actual production.)

1. The utility model provides an etching solution of thick molybdenum plate, is applied to the accurate fretwork etching to thick molybdenum plate which characterized in that: measured by volume, contains 10 to 15 percent of H₂SO₄、20％～35% HNO₃And 5-10% of organic additive containing ether bond, and the balance of H₂O。

2. The etching solution for thick molybdenum plates according to claim 1, wherein: measured by volume, contains 11 to 14 percent of H₂SO₄22 to 32 percent of HNO₃6 to 9 percent of organic additive containing ether bond, and the balance of H₂O。

3. The etching solution for thick molybdenum plates according to claim 2, wherein: measured by volume, contains 12 to 13 percent of H₂SO₄25 to 30 percent of HNO₃7 to 8 percent of organic additive containing ether bond, and the balance of H₂O。

4. The etching solution for thick molybdenum plates according to claim 3, wherein: measured by volume, contains 12.5% of H₂SO₄27% of HNO₃And 7.5% of organic additive containing ether bond, and the balance of H₂O。

5. The etching solution for thick molybdenum plates according to claim 1, wherein: said H₂SO₄The mass fraction of (A) is 95-98%.

6. The etching solution for thick molybdenum plates according to claim 1, wherein: the HNO₃The mass fraction of (A) is 65-68%.

7. The etching solution for thick molybdenum plates according to claim 1, wherein: the ether bond-containing organic additive is fatty alcohol-polyoxyethylene ether and/or alkylphenol polyoxyethylene ether.

8. The etching solution for thick molybdenum plates according to claim 1, wherein: said H₂And O is deionized water.

9. A method for preparing an etching solution for thick molybdenum plates according to any one of claims 1 to 8, characterized in that: the preparation steps are as follows:

s1. measuring H₂O to a liquid preparation container;

s2, adding H into the liquid preparation container in a grading manner₂SO₄Continuously stirring;

s3, adding HNO after the temperature of the solution is reduced to room temperature₃Adding into a liquid preparation container, and continuously stirring;

and S4, after the temperature of the solution is reduced to room temperature, adding the organic additive containing ether bonds into the solution preparation container, and continuously stirring.

10. The method of preparing an etching solution for a thick molybdenum plate according to claim 9, wherein: in step S2, H is added₂SO₄When the temperature of the solution is controlled to be less than 60 ℃.

Technical Field

The application relates to the technical field of molybdenum plate etching, in particular to etching solution for a thick molybdenum plate and a preparation method thereof.

Background

Chemical etching is a special processing method, does not introduce defects such as stress and burrs to a substrate, has the advantages of high processing efficiency and high precision, and has mature application in processing metals such as stainless steel, copper, aluminum and the like.

The molybdenum metal has the physical and chemical properties of high melting point, high strength, no magnetism, small thermal expansion coefficient, corrosion resistance and the like, and the product is widely applied to the aerospace and semiconductor industries. The precise chemical etching of molybdenum presents a high technical difficulty since molybdenum is resistant to corrosion and its corrosion product state is different from that of conventional metals. Particularly, in the etching of a thick molybdenum plate (a metal plate with a plate thickness of more than 0.20mm), the thicker the plate thickness is, the larger the etching depth is, the more difficult the technology for realizing precise etching is, and the current technology suitable for trace (etching amount is below micron) etching processing is no longer effective for the thick molybdenum plate. For thick molybdenum plates, the etching technology is mainly used for researching the formula of the etching solution.

The existing molybdenum etching solution generally comprises nitric acid, other inorganic acid (one of sulfuric acid, hydrochloric acid and phosphoric acid), water and nitrate, and has the following problems when being applied to molybdenum plate etching processing:

1) nitric acid is the major component and the etch rate is sensitive to nitric acid concentration. When the concentration of the nitric acid is too high (vol% > 40%), the corrosion rate is high, the etching process is not easy to control, the etching texture is rough, and the requirement of a high-precision etching product on the dimensional precision (within the dimensional deviation +/-0.05 mm) is further influenced; when the concentration of nitric acid is low (vol% < 20%) the etch rate is very slow, making production very inefficient and side etch evident (etch factor requirement typically > 5).

2) In the etching process, when the metal matrix under the corrosion-resistant film layer is compensated and expanded, the etching amount of the metal plate surface is easy to be uneven in each direction, the etching effect shows anisotropy, and the requirement of a high-precision etching product on isotropy (the difference of the etching amount in each direction is less than 0.01mm) cannot be met.

3) The concentration change caused by the chemical corrosion consumption, decomposition, volatilization and the like of the nitric acid can cause the fluctuation of the product quality and is not beneficial to batch production.

Disclosure of Invention

The first purpose of the application is to provide an etching solution for a thick molybdenum plate, which can ensure uniform etching shading and small side etching when the thick molybdenum plate is etched; the method can ensure that the molybdenum etching product has better dimensional accuracy and dimensional uniformity; and can be suitable for batch production in actual production.

A second object of the present invention is to provide a method for preparing an etching solution for a thick molybdenum plate, which can rapidly and stably produce the etching solution for a thick molybdenum plate.

The embodiment of the application is realized by the following technical scheme:

an etching solution for thick molybdenum plate, which is used for precise hollow etching of the thick molybdenum plate and contains 10-15% of H by volume₂SO₄20 to 35 percent of HNO₃And 5-10% of organic additive containing ether bond, and the balance of H₂O。

Further, the hydrogen-containing composition contains 11 to 14 percent of H by volume₂SO₄22 to 32 percent of HNO₃6 to 9 percent of organic additive containing ether bond, and the balance of H₂O。

Further, the hydrogen-containing composition contains 12 to 13 percent of H by volume₂SO₄25 to 30 percent of HNO₃7 to 8 percent of organic additive containing ether bond, and the balance of H₂O。

Further, it contained 12.5% by volume of H₂SO₄27% of HNO₃And 7.5% of organic additive containing ether bond, and the balance of H₂O。

Further, said H₂SO₄The mass fraction of (A) is 95-98%.

Further, the HNO₃The mass fraction of (A) is 65-68%.

Further, the ether bond-containing organic additive is fatty alcohol-polyoxyethylene ether and/or alkylphenol polyoxyethylene ether.

Further, said H₂And O is deionized water.

The preparation method of the etching solution for the thick molybdenum plate comprises the following preparation steps:

s1. measuring H₂O to a liquid preparation container;

s2, adding H into the liquid preparation container in a grading manner₂SO₄Continuously stirring;

s3, adding HNO after the temperature of the solution is reduced to room temperature₃Adding into a liquid preparation container, and continuously stirring;

and S4, after the temperature of the solution is reduced to room temperature, adding the organic additive containing ether bonds into the solution preparation container, and continuously stirring.

Further, in step S2, H is added₂SO₄When the temperature of the solution is controlled to be less than 60 ℃.

The technical scheme of the embodiment of the application has at least the following advantages and beneficial effects:

the etching solution provided by the application is added with the ether bond-containing organic additive, and has a gain effect on the isotropy of etching of a base body under a corrosion-resistant ink layer, so that a molybdenum etching product is ensured to have high size precision and size uniformity, under the synergistic effect of each component and the content of the component, the etching of a thick molybdenum plate (the thickness is more than 0.20mm) can be completed, and a precision etching molybdenum metal plate product with uniform shading, small side etching, high size precision and size uniformity can be produced in batch, the defective rate is low, and the product quality meets the use requirements of aerospace devices and semiconductor equipment.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The etching solution for a thick molybdenum plate and the preparation method thereof provided by the embodiments of the present invention are specifically described below.

An etching solution for thick molybdenum plate, which is used for precise hollow etching of the thick molybdenum plate and contains 10-15% of H by volume₂SO₄20 to 35 percent of HNO₃And 5-10% of organic additive containing ether bond, and the balance of H₂O, specifically, H₂SO₄Can be 10%, 11%, 12%, 13%, 14%, 15% of H₂SO₄，HNO₃May be 20%, 22%, 24%, 26%, 28%, 30%, 32%, 35% HNO₃The ether bond-containing organic additive may be 5%, 6%, 7%, 8%, 9%, 10% of an ether bond-containing organic additive, wherein H is₂SO₄Is 95-98 percent, and optionally, H₂SO₄95%, 96%, 97%, 98% by mass of HNO₃65-68% of (C), optionally HNO₃The mass fractions of 65%, 66%, 67% and 68% of the total weight of the organic additive are respectively fatty alcoholPolyoxyethylene ethers and/or alkylphenol ethoxylates, H₂And O is deionized water.

A preparation method of the etching solution for the thick molybdenum plate comprises the following preparation steps:

s1. measuring H₂O to a liquid preparation container;

s2, adding H into the liquid preparation container in a grading manner₂SO₄Continuously stirring; it should be noted that, in the case of adding H₂SO₄In the whole process, the temperature needs to be controlled below 60 ℃;

s3, adding HNO after the temperature of the solution is reduced to room temperature₃Adding into a liquid preparation container, and continuously stirring;

s4, when the temperature of the solution is reduced to room temperature, adding the organic additive containing ether bonds into the solution preparation container, and continuously stirring.