CN114870740B

CN114870740B - Production system and method for displaying process metal ion acidic etching solution

Info

Publication number: CN114870740B
Application number: CN202210502822.4A
Authority: CN
Inventors: 邵振; 陈杰
Original assignee: Jiangsu Heda Electronic Technology Co ltd
Current assignee: Jiangsu Heda Electronic Technology Co ltd
Priority date: 2022-05-10
Filing date: 2022-05-10
Publication date: 2023-06-30
Anticipated expiration: 2042-05-10
Also published as: CN114870740A

Abstract

The invention provides a production system and a production method for a metal ion acidic etching solution for a display process, wherein the production system comprises a heater for performing temperature programming through PLC control, the heater is used for performing temperature programming on an etching solution premixed raw material and an additive, the etching solution premixed raw material comprises acid, alkali and metal inorganic salt, the rapid heat exchanger is connected with the heater and is used for rapidly exchanging heat for the etching solution premixed raw material after the temperature programming of the heater, the hydrogen peroxide mixing tank is connected with the rapid heat exchanger and is used for mixing the etching solution premixed raw material after the rapid heat exchange of the rapid heat exchanger with hydrogen peroxide, and the etching effect and the side etching effect of the metal ion acidic etching solution for the display process, which is prepared by adopting temperature programming, are more stable than those of the metal ion acidic etching solution for the display process, which is not used for temperature programming.

Description

Production system and method for displaying process metal ion acidic etching solution

Technical Field

The invention belongs to the technical field of etching solutions, and particularly relates to a production system and a production method for an acidic etching solution for displaying metal ions in a process.

Background

The etching liquid is a raw material for engraving drypoint. A liquid for engraving by eroding the characteristics of the material. There are six types of etching solutions that have been used: acidic copper chloride, alkaline copper chloride, ferric chloride, ammonium persulfate, sulfuric acid/chromic acid, sulfuric acid/hydrogen peroxide etching solution.

Because the process conditions in the prior art are not mature enough, the components of the prepared etching solution are unstable, the proportion of the components in the etching solution is changed continuously, so that the specific gravity, the concentration of free hydrogen ions and other parameters of the etching solution are required to be detected continuously, the addition amount of each component is controlled in real time, the stable etching rate of the produced etching solution can be ensured, the operation difficulty is high when the addition amount of each component is controlled, the process conditions of the production of the etching solution are controlled when the etching solution is produced, and the change of the proportion of the components in the prepared etching solution is avoided, so that the stable etching rate and the side etching rate are the problems to be solved urgently.

Disclosure of Invention

The present invention is directed to a system and a method for producing an acidic etching solution for displaying a metal ion in a process, so as to solve the problem of maintaining a stable etching rate and a stable side etching rate by controlling the process conditions of the etching solution production in the above-mentioned background art.

In order to achieve the above purpose, the present invention provides the following technical solutions:

a production system for displaying a process metal ion acidic etching solution, which is characterized in that: the production system for the metal ion acidic etching solution used for displaying the processing procedure comprises:

-a heater for programmed heating by PLC control, said heater programmed heating an etching solution premix material and an additive, wherein the etching solution premix material comprises an acid, an alkali, a metal inorganic salt, wherein said additive in the present invention is other substances excluding the acid, the alkali, the metal inorganic salt and hydrogen peroxide, the additive may be a combination of a plurality of substances;

-a rapid heat exchanger connected to the heater for rapid heat exchange of the pre-mixed raw material of the etching solution after temperature programming of the heater;

-a hydrogen peroxide mixing tank connected to the rapid heat exchanger for mixing the etching solution after rapid heat exchange of the rapid heat exchanger with hydrogen peroxide.

As a further improvement, further comprising:

an acid-base mixing tank connected with the heater, an acid mixing tank and an alkali mixing tank respectively connected with the acid-base mixing tank,

the acid mixing tank is used for mixing acid, the alkali mixing tank is used for mixing alkali, and the acid-alkali mixing kettle is used for mixing the acid in the acid mixing tank and the alkali in the alkali mixing tank;

-a second ultrasonic device connected with the hydrogen peroxide mixing tank, and a filtering system connected with the second ultrasonic device, wherein the second ultrasonic device and the filtering system are used for carrying out ultrasonic treatment and filtering on substances in the hydrogen peroxide mixing tank;

-a first sonicator disposed between the acid mixing tank and the acid-base mixing tank, the first sonicator configured to sonicate the acid in the acid mixing tank.

A production method for an acidic etching solution for displaying metal ions in a manufacturing process is characterized by comprising the following steps: the method comprises the following steps:

step 1: feeding the premixed etching solution raw material and the additive into a heater, controlling the temperature at 30-45 ℃, and repeatedly circulating for 1-3h (for example, every 1h, 2h, 3h and the like);

step 2: the material in the step 1 is subjected to temperature programming, wherein the temperature programming comprises two stages, the first stage is heated from 30-45 ℃ to 45-60 ℃, and the second stage is heated from 45-60 ℃ to 65-75 ℃;

step 3: delivering the substances in the step 2 into a rapid heat exchanger for cooling treatment;

step 4: and (3) conveying the substances in the step (3) into a hydrogen peroxide mixing tank, adding hydrogen peroxide, and uniformly mixing to obtain a finished product.

As a further improvement, the first stage in the step 2 is kept at a constant temperature for 7-13 hours after the temperature is raised from 30-45 ℃ to 45-60 ℃, and the second stage is kept at a constant temperature for 7-13 hours after the temperature is raised from 45-60 ℃ to 65-75 ℃.

As a further improvement, the temperature is increased from 30-45 ℃ to 45-60 ℃ in the step 2, and the temperature is increased for 0-3h.

As a further improvement, the temperature is raised from 45-60 ℃ to 65-75 ℃ in the step 2, and the temperature is raised for 0-1h.

As a further improvement, the temperature in the step 3 is reduced from 65-75 ℃ to 20-30 ℃ and the residence time is 60-240s.

As a further improvement, the etching solution premix raw material in step 1 is prepared by the following steps:

1.1, adding acid into a pretreated acid mixing tank, stirring at a stirring speed of 100-200r/min for more than 30min (for example, every 30min, 60min, 1.5h, 2h and the like), and performing ultrasonic treatment by a first ultrasonic device for 20-50s;

1.2, adding the alkali into an alkali mixing tank, and stirring for more than 30min (stirring for example every 30min, 1h, 1.5h, 2h and the like);

1.3, adding metal inorganic salt into the step 1.2, and stirring for more than 30min (stirring for example, every 30min, 60min, 1.5h, 2h and the like);

1.4, adding the substances in the steps 1.1 and 1.3 into a pretreated acid-base mixing kettle, stirring at a speed of 80-150r/min, stirring for more than 4 hours (for example, every 4 hours, 5 hours, 6 hours and the like), and refluxing to obtain an etching solution premix raw material.

As a further improvement, the pretreatment is performed in the acid mixing tank 4 in the step 1.1 with ultrapure water, and the pretreatment is performed in the acid-base mixing tank 6 in the step 1.4 with inert gas.

As a further improvement, the substance in the step 4 is filtered by a second ultrasonic device for 40-90s and a filtering system.

Compared with the prior art, the invention has the beneficial effects that: in the production system and the method for the metal ion acidic etching liquid for the display process, when the etching liquid is prepared, the etching liquid prepared by using the programmed temperature rise has more stable etching rate and side etching rate than the etching liquid prepared by not using the programmed temperature rise by controlling the process conditions of the etching liquid production, so that the problem of unstable etching rate and side etching rate of the etching liquid caused by continuously changing the component proportion in the etching liquid in the storage process of the etching liquid is avoided.

Drawings

FIG. 1 is a schematic diagram of a system and method for producing an acidic etching solution with metal ions according to the present invention.

In the figure: 1-filtration system, 2-alkali mixing tank, 3-hydrogen peroxide mixing tank, 4-acid mixing tank, 5-first ultrasonic device, 6-acid alkali mixing kettle, 7-heater, 8-quick heat exchanger, 9-second ultrasonic device.

Detailed Description

The present invention is further illustrated in the following drawings and detailed description, which are to be understood as being merely illustrative of the invention and not limiting the scope of the invention.

As shown in fig. 1, a production system for displaying a process metal ion acidic etching solution, the production system for displaying a process metal ion acidic etching solution comprising:

a heater 7 for programmed heating by PLC control, said heater 7 programmed heating the etching solution premix and the additive, wherein the etching solution premix comprises acid, alkali, metal inorganic salt;

-a rapid heat exchanger 8, the rapid heat exchanger 8 being connected to the heater 7 for rapid heat exchange of the pre-mixed raw material of the etching solution after the temperature programming of the heater 7;

-a hydrogen peroxide mixing tank 3, wherein the hydrogen peroxide mixing tank 3 is connected with the rapid heat exchanger 8 and is used for premixing the etching solution after rapid heat exchange of the rapid heat exchanger 8 with hydrogen peroxide.

Further comprises:

an acid-base mixing tank 6 connected with a heater 7, and an acid mixing tank 4 and a base mixing tank 2 respectively connected with the acid-base mixing tank 6,

the acid mixing tank 4 is used for mixing acid, the alkali mixing tank 2 is used for mixing alkali, and the acid-alkali mixing kettle 6 is used for mixing the acid in the acid mixing tank 4 and the alkali in the alkali mixing tank 2;

a second ultrasonic device 9 connected with the hydrogen peroxide mixing tank 3, and a filtering system 1 connected with the second ultrasonic device 9, wherein the second ultrasonic device 9 and the filtering system 1 are used for carrying out ultrasonic treatment and filtering on substances in the hydrogen peroxide mixing tank 3;

a first sonicator 5 placed between the acid mixing tank 4 and the acid-base mixing tank 6, said first sonicator 5 being used to sonicate the acid in the acid mixing tank 4.

When the etching solution is produced by a production system for displaying the process etching solution, the production method comprises the following production processes:

the etching solution premixed raw material is conveyed into a heater 7 through a conveying pump, an additive is added into the heater 7, after the reciprocating circulation is carried out for 1-3 hours, the heater 7 is subjected to temperature programming, the temperature programming comprises two stages, the first stage is used for heating the substances in the step 2 from 30-45 ℃ to 45-60 ℃, the second stage is used for heating the substances from 45-60 ℃ to 65-75 ℃, the substances subjected to the temperature programming are conveyed into a rapid heat exchanger 8 through the conveying pump for cooling treatment, and the temperature is reduced from 65-75 ℃ to 20-30 ℃ and the residence time is 60-240s;

and (3) conveying the substances subjected to cooling treatment into a hydrogen peroxide mixing tank 3 through a conveying pump, adding hydrogen peroxide and uniformly mixing to obtain a finished product.

Wherein, the etching solution premix raw material in the step 1 is prepared by the following steps:

adding ultrapure water into an acid mixing tank 4, adding acid into the acid mixing tank 4 containing ultrapure water, stirring at a stirring speed of 100-200r/min, stirring for more than 30min, and carrying out ultrasonic treatment on the acid in the acid mixing tank 4 by a first ultrasonic device 5 for 20-50s;

adding alkali into the alkali mixing tank 2, stirring for more than 30min, adding metal inorganic salt into the alkali mixing tank 2, and stirring for more than 30min;

firstly, protecting the inside of an acid-base mixing kettle 6 by inert gas, controlling the temperature in the acid-base mixing kettle 6 to be 30-45 ℃, then respectively conveying the acid after ultrasonic treatment of a first ultrasonic device 5 and alkali and metal inorganic salt in an alkali mixing tank 2 into the acid-base mixing kettle 6 through a conveying pump, stirring for more than 4 hours, refluxing, and stirring at the rotating speed of 80-150r/min to obtain the premixed etching liquid raw material.

Wherein, the temperature programming comprises two stages, the first stage can also heat the substances in the step 2 to 45-60 ℃ and keep the temperature for 7-13h, and the second stage can heat the substances from 45-60 ℃ to 65-75 ℃ and keep the temperature for 7-13h.

In the temperature programming, the temperature in the step 2 can be raised from 30-45 ℃ to 45-60 ℃ for 1-3 hours.

In the temperature programming, the temperature in the step 2 can be raised from 45-60 ℃ to 65-75 ℃ for 0-1h.

Wherein, substances in the hydrogen peroxide mixing tank 3 can be respectively filtered by a second ultrasonic device 9 for 40-90s and a filtering system 1 with the aperture of 0.4-0.9 mu m to obtain a finished product.

The invention relates to a production system and a method for preparing etching solution added with hydrogen peroxide.

The metal ions in the metal inorganic salt are one or a combination of a plurality of potassium, sodium, magnesium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, cadmium, indium, tin, calcium and zirconium, and the anions in the metal inorganic salt are one or a combination of a plurality of sulfate radicals, nitrate radicals, bicarbonate radicals, sulfite radicals, hexafluorosilicate radicals, hexacyanoferrate radicals, sulfide ions, fluoride ions, silicate radicals, chloride ions and ammonium ions.

The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.

Example 1-1:

the etching solution CTK6000D is taken as a production object, and the etching solution is produced by adopting the following method, which specifically comprises the following steps:

step 1: conveying the premixed etching liquid raw material into a heater, adding EDTA, methylsulfonic acid and phenylurea into the heater, and circulating for 2 hours in a reciprocating manner;

step 2: the temperature programming of the substances in the heater in the step 1 is carried out, wherein the temperature programming comprises two stages, the substances in the step 1 are heated to 60 ℃ in the first stage, the temperature is raised for 1h, the temperature is kept for 12 h, the temperature is raised to 70 ℃ from 60 ℃ in the second stage, the temperature is raised for 0h, and the temperature is kept for 8 h;

step 3: delivering the substances in the step 2 into a rapid heat exchanger for cooling treatment, wherein the temperature is reduced from 70 ℃ to 30 ℃ and the residence time is 160s;

1.1, adding citric acid into a pretreated acid mixing tank 4, slowly adding sulfuric acid, wherein the sulfuric acid concentration is 17%, the sulfuric acid adding speed is 16L/min, stirring is carried out while adding, the stirring speed is 150r/min, after the sulfuric acid is completely added, continuing stirring for 1h, and then carrying out ultrasonic treatment on the acid in the acid mixing tank 4 for 30s through a first ultrasonic device 5;

1.2, adding ammonia water, p-phenylenediamine and triethanolamine into an alkali mixing tank 2, and stirring for 1h;

1.3, adding ferric trichloride into an alkali mixing tank 2 for adding alkali, and continuously stirring for 1.5 hours;

1.4, conveying the substances in the steps 1.1 and 1.3 into a pretreated acid-base mixing kettle, stirring for 5 hours and refluxing, wherein the stirring speed is 100r/min.

Wherein, the acid mixing tank (4) in the step 1.1 is pretreated by ultrapure water, the acid-base mixing kettle (6) in the step 1.4 is pretreated by inert gas, and the temperature in the acid-base mixing kettle 6 is controlled at 40 ℃;

and (3) respectively carrying out ultrasonic treatment on the substances in the step (4) by a second ultrasonic device for 60 seconds and filtering by a filtering system with the aperture of 0.5 mu m to obtain a finished product.

Examples 1-2:

the production object used is the same as in example 1, and the production method is basically the same as in example 1, except that: and 9, heating the first stage in the step 8 for 2h, heating the second stage for 0h, and heating other conditions the same.

Examples 1-3:

the production object used is the same as in example 1, and the production method is basically the same as in example 1, except that: and 9, heating the first stage in the step 8 for 3h, heating the second stage for 0h, and heating other conditions the same.

Examples 1 to 4:

the production object used is the same as in example 1, and the production method is basically the same as in example 1, except that: and 9, heating the first stage in the step 8 for 0h, heating the second stage for 1h, and heating other conditions the same.

Examples 1 to 5:

the production object used is the same as in example 1, and the production method is basically the same as in example 1, except that: step 9 is to raise the temperature of the first stage of step 8 for 1h, and raise the temperature of the second stage for 1h, and other temperature raising conditions are the same.

Examples 1 to 6:

the production object used is the same as in example 1, and the production method is basically the same as in example 1, except that: and 9, heating the first stage in the step 8 for 2h, heating the second stage for 1h, and heating other conditions the same.

Examples 1 to 7:

the production object used is the same as in example 1, and the production method is basically the same as in example 1, except that: and 9, heating the first stage in the step 8 for 3h, heating the second stage for 1h, and heating other conditions the same.

Comparative examples 1-1:

the production object used is the same as in example 1, and the production method is basically the same as in example 1, except that: step 9 is to heat the material in the heater in step 8 to 70 ℃ and keep the temperature for 20 hours.

Example 2-1:

in this embodiment, the following etching solution is used as the production object:

material name	Percentage mass/%
		Hydrogen peroxide	18
Ammonia fluoride	0.2
		Nitric acid	7.1
Tetramethyl ammonium hydroxide	16
		Phenylureas	0.5
3-aminotriazole	0.3
		Ferric trichloride	2
Water and its preparation method	55.9

The etching solution is produced by adopting the following method, which specifically comprises the following steps:

step 1: the premixed etching solution raw material is conveyed into a heater, 3-aminotriazole and ammonia fluoride are added into the heater, and the reciprocating circulation is carried out for 3 hours;

step 2: the temperature programming of the substances in the heater in the step 1 is carried out, wherein the temperature programming comprises two stages, the substances in the step 1 are heated to 60 ℃ in the first stage, the temperature is raised for 1h, the temperature is kept for 13h, the temperature is raised to 75 ℃ from 60 ℃ in the second stage, the temperature is raised for 0h, and the temperature is kept for 13 h;

step 3: delivering the substances in the step 2 into a rapid heat exchanger for cooling treatment, wherein the temperature is reduced from 75 ℃ to 30 ℃ and the residence time is 240s;

step 4: conveying the substances in the step 3 into a hydrogen peroxide mixing tank, adding hydrogen peroxide, and uniformly mixing to obtain a finished product;

1.1: adding nitric acid into the pretreated acid mixing tank 4, stirring at the stirring speed of 200r/min for 2h, and carrying out ultrasonic treatment on the acid in the acid mixing tank 4 for 50s through a first ultrasonic device 5;

1.2: adding phenylurea and tetramethylammonium hydroxide into the alkali mixing tank 2, and stirring for 2 hours;

1.3: adding copper sulfate into the alkali mixing tank 2 with alkali, and continuously stirring for 2 hours;

1.4, conveying the substances in the steps 1.1 and 1.3 into a pretreated acid-base mixing kettle, stirring for 6 hours, refluxing, and stirring at a speed of 150r/min;

wherein, the acid mixing tank (4) in the step 1.1 is pretreated by ultrapure water, the acid-base mixing kettle (6) in the step 1.4 is pretreated by inert gas, and the temperature in the acid-base mixing kettle 6 is controlled at 45 ℃;

and (3) respectively carrying out ultrasonic treatment on the substances in the step (4) by a second ultrasonic device for 90 seconds and filtering by a filtering system with the aperture of 0.9 mu m to obtain a finished product.

Example 2-2:

the production object used is the same as in example 2, and the production method is basically the same as in example 2, except that: and 9, heating the first stage in the step 8 for 2h, heating the second stage for 0h, and heating other conditions the same.

Examples 2-3:

the production object used is the same as in example 2, and the production method is basically the same as in example 2, except that: and 9, heating the first stage in the step 8 for 3h, heating the second stage for 0h, and heating other conditions the same.

Examples 2 to 4:

the production object used is the same as in example 2, and the production method is basically the same as in example 2, except that: and 9, heating the first stage in the step 8 for 0h, heating the second stage for 1h, and heating other conditions the same.

Examples 2 to 5:

the production object used is the same as in example 2, and the production method is basically the same as in example 2, except that: step 9 is to raise the temperature of the first stage of step 8 for 1h, and raise the temperature of the second stage for 1h, and other temperature raising conditions are the same.

Examples 2 to 6:

the production object used is the same as in example 2, and the production method is basically the same as in example 2, except that: and 9, heating the first stage in the step 8 for 2h, heating the second stage for 1h, and heating other conditions the same.

Examples 2 to 7:

the production object used is the same as in example 2, and the production method is basically the same as in example 2, except that: and 9, heating the first stage in the step 8 for 3h, heating the second stage for 1h, and heating other conditions the same.

Comparative example 2-1:

the production object used is the same as in example 2, and the production method is basically the same as in example 2, except that: step 9 is to heat the material in the heater in step 8 to 75 ℃ and keep the temperature for 26 hours.

Example 3-1:

material name	Percentage mass/%
		Zinc chloride	1.1
Propionic acid	0.7
		Malic acid	8
Malonic acid	10
		Tartaric acid	0.6
Acrylic acid	0.3
		N-methylaniline	1.1
Dimethylethanolamine	3
		Phenylureas	0.7
Tetramethyl ammonium hydroxide	2
		Triethanolamine salt	0.8
Hydrogen peroxide	20
		Water and its preparation method	51.7

step 1: the premixed etching solution raw material is conveyed into a heater, benzotriazole is added into the heater, and the reciprocating circulation is carried out for 1 hour;

step 2: the temperature programming of the substances in the heater in the step 1 is carried out, wherein the temperature programming comprises two stages, the substances in the step 1 are heated to 45 ℃ in the first stage, the temperature is raised for 1h, the temperature is kept for 7 h, the temperature is raised to 65 ℃ from 45 ℃ in the second stage, the temperature is raised for 0h, and the temperature is kept for 7 h;

step 3: delivering the substances in the step 2 into a rapid heat exchanger for cooling treatment, wherein the temperature is reduced from 65 ℃ to 20 ℃ and the residence time is 60s;

1.1, adding propionic acid, malic acid, malonic acid, tartaric acid and acrylic acid into a pretreated acid mixing tank 4, stirring while adding, wherein the stirring speed is 100r/min, continuously stirring for 30min after the sulfuric acid is completely added, and carrying out ultrasonic treatment on the acid in the acid mixing tank 4 for 20s by a first ultrasonic device 5;

1.2, adding N-methylaniline, dimethylethanolamine, phenylurea, tetramethylammonium hydroxide and triethanolamine into a base mixing tank 2, and stirring for 30min;

1.3, adding zinc chloride into the alkali mixing tank 2 with alkali, and continuously stirring for 30min;

1.4, conveying the substances in the steps 1.1 and 1.3 into an acid-base mixing kettle, stirring for 4 hours, refluxing, and stirring at a speed of 80r/min.

Wherein, the acid mixing tank (4) in the step 1.1 is pretreated by ultrapure water, the acid-base mixing kettle (6) in the step 1.4 is pretreated by inert gas, and the temperature in the acid-base mixing kettle 6 is controlled at 30 ℃;

and 4, respectively carrying out ultrasonic treatment on the substances in the step 4 by a second ultrasonic device for 40s and filtering the substances with the aperture of 0.4 mu m by a filtering system to obtain a finished product.

Example 3-2:

the production object used is the same as in example 3, and the production method is basically the same as in example 3, except that: and 9, heating the first stage in the step 8 for 2h, heating the second stage for 0h, and heating other conditions the same.

Examples 3-3:

the production object used is the same as in example 3, and the production method is basically the same as in example 3, except that: and 9, heating the first stage in the step 8 for 3h, heating the second stage for 0h, and heating other conditions the same.

Examples 3-4:

the production object used is the same as in example 3, and the production method is basically the same as in example 3, except that: and 9, heating the first stage in the step 8 for 0h, heating the second stage for 1h, and heating other conditions the same.

Examples 3 to 5:

the production object used is the same as in example 3, and the production method is basically the same as in example 3, except that: step 9 is to raise the temperature of the first stage of step 8 for 1h, and raise the temperature of the second stage for 1h, and other temperature raising conditions are the same.

Examples 3 to 6:

the production object used is the same as in example 3, and the production method is basically the same as in example 3, except that: and 9, heating the first stage in the step 8 for 2h, heating the second stage for 1h, and heating other conditions the same.

Examples 3 to 7:

the production object used is the same as in example 3, and the production method is basically the same as in example 3, except that: and 9, heating the first stage in the step 8 for 3h, heating the second stage for 1h, and heating other conditions the same.

Comparative example 3-1:

the production object used is the same as in example 1, and the production method is basically the same as in example 3, except that: step 9 is to heat the material in the heater in step 8 to 65 ℃ and keep the temperature for 14 hours.

Example 1 etching target was a copper-molybdenum coupon whose composition was copper and molybdenum, and copper layer film thickness

Molybdenum layer film thickness->

The size of the copper-molybdenum test piece is 1cm ² The etching time was 290s and the etching temperature was 32 ℃.

Comparative example 1 etching object the same as in example 1.

Example 2 copper titanium coupon to be etched, the copper titanium coupon contains copper and titanium, and the copper layer has a thickness

Titanium layer film thickness->

The size of the copper-titanium test piece is 1cm ² The etching time was 120s and the etching temperature was 32 ℃.

Comparative example 2 etching object the same as in example 2.

Example 3 the etching object was the same as in example 1.

Comparative example 3 etching object the same as in example 1.

CD-bias, taper and copper bearing capacities were tested on the etching solutions prepared in examples 1-1 to 1-7, examples 2-1 to 2-7, examples 3-1 to 3-7 and comparative examples 1-1 to 1-3, wherein the CD-bias measured value was in accordance with the production requirement at 0.6 to 1.5 μm, the Taper measured value was in accordance with the production requirement at 35℃to 50℃and the copper bearing capacity was in accordance with the production requirement at not less than 6000ppm, wherein the etching solutions prepared in examples 1-1 to 1-7, examples 2-1 to 2-7, examples 3-1 to 3-7 and comparative examples 1-1 to 1-3 were etching solutions stored for one month, and the test data were shown in Table 1:

TABLE 1

As is clear from the analysis of Table 1, the copper bearing capacity, CD-bias and Taper were low when the temperature was not raised in the second stage of examples 1-1 to 1-3, the number of active sites was small, the etching activity was poor, the etching angle was small, CD was small, the reaction was hardly caused, the copper bearing capacity, CD-bias and Taper were high when the temperature was raised in the second stage of examples 1-4 to 1-7, the etching effect was good, the copper bearing capacity, CD-bias and Taper were good when the temperature was raised in the first stage of examples 1-6, the copper bearing capacity, CD-bias and Taper were best when the temperature was not raised in the first stage of comparative examples 1-7 and 1-1, the copper bearing capacity of comparative examples 1-1 was lowest when the temperature was not raised in the first stage of comparative examples 1-1, the CD-bias and Taper were low, the etching activity was poor, the etching angle was small, and the reaction was hardly caused.

Similarly, when the temperature is not raised in the second stage of examples 2-1 to 2-3, the copper bearing capacity, CD-bias and per are low, the active sites are few, the etching activity is poor, the etching is slow, the angle is small, CD is small, the reaction is hardly caused, when the temperature is raised in the second stage of examples 2-4 to 2-7, the copper bearing capacity, CD-bias and per are improved, the etching effect is good, and when the copper bearing capacity, CD-bias and per are in the second stage of examples 2-6, the etching effect is best, and when the temperature is not raised in the first stage of comparative example 2-1, the copper bearing capacity of comparative example 2-1 is lowest, and the CD-bias and per are low, the active sites are few, the etching activity is poor, the etching is slow, the angle is small, and the reaction is hardly caused, as can be seen from the comparison analysis of the first stage of comparative example 2-7 and the comparative example 2-1.

Similarly, when the temperature is not raised in the second stage of examples 3-1 to 3, the copper bearing capacity, CD-bias and per are low, the active sites are few, the etching activity is poor, the etching is slow, the angle is small, the CD is small, the reaction is hardly caused, when the temperature is raised in the second stage of examples 3-4 to 3-7, the copper bearing capacity, CD-bias and per are improved, the etching effect is good, and when the copper bearing capacity, CD-bias and per are in the second stage of examples 3-6, the etching effect is best, and when the temperature is not raised in the first stage of comparative example 3-1, the copper bearing capacity of comparative example 3-7 is lowest, and the CD-bias and per are low, the active sites are few, the etching activity is poor, the etching is slow, the angle is small, and the reaction is hardly caused, as can be seen from the comparison analysis of the first stage of comparative example 3-7 and the comparative example 3-1.

Further, it was found from the analysis and comparison of examples 1 to 3, examples 2 to 3 and examples 3 to 3 that metal remained at the time of raising the temperature for 3 hours, and that the etching was incomplete and the etching effect was poor.

Therefore, when the metal ion acidic etching solution containing hydrogen peroxide is produced, the copper bearing capacity, CD-bias, super and metal residues of the metal ion acidic etching solution can be influenced by setting the temperature programming under the condition of the same additive components, so that the etching effect of the etching solution is influenced, and the problem of unstable etching rate and side etching rate of the etching solution caused by continuously changing the component ratio of the etching solution in storage is avoided.

It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents, it being apparent that the described embodiments of the invention are only some of the embodiments of the invention and not all the embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Claims

1. A production method for an acidic etching solution for displaying metal ions in a manufacturing process is characterized by comprising the following steps: the method comprises the following steps:

step 1: the premixed raw material of the etching solution and the additive are conveyed into a heater (7), the temperature is controlled at 30-45 ℃, and the reciprocating circulation is carried out for 1-3h;

step 3: conveying the substances in the step 2 into a rapid heat exchanger (8) for cooling treatment;

step 4: conveying the substances in the step 3 into a hydrogen peroxide mixing tank (3), adding hydrogen peroxide, and uniformly mixing to obtain a finished product;

in the step 2, the temperature is raised from 30-45 ℃ to 45-60 ℃ in the first stage, the temperature is kept for 7-13 hours, and the temperature is raised from 45-60 ℃ to 65-75 ℃ in the second stage, and the temperature is kept for 7-13 hours;

in the step 2, the temperature is raised from 30-45 ℃ to 45-60 ℃ for 1-3h;

in the step 2, the temperature is raised from 45-60 ℃ to 65-75 ℃ for 1h;

the etching solution premix raw material in the step 1 is prepared by the following steps:

1.1, adding acid into a pretreated acid mixing tank (4), stirring at a speed of 100-200r/min for more than 30min, and performing ultrasonic treatment by a first ultrasonic device (5) for 20-50s;

1.2, adding alkali into the alkali mixing tank (2), and stirring for more than 30 minutes;

1.3, adding metal inorganic salt into the step 1.2, and stirring for more than 30 minutes;

1.4, adding the substances in the steps 1.1 and 1.3 into a pretreated acid-base mixing kettle (6), stirring at a speed of 80-150r/min, stirring for more than 4 hours, and refluxing to obtain the etching solution premix.

2. The method of claim 1, wherein the step of producing the metal ion acidic etching solution comprises: in the step 3, the temperature is reduced from 65-75 ℃ to 20-30 ℃ and the residence time is 60-240s.

3. The method of claim 1, wherein the step of producing the metal ion acidic etching solution comprises: the acid mixing tank (4) in the step 1.1 is pretreated by ultrapure water, and the acid-base mixing tank (6) in the step 1.4 is pretreated by inert gas.

4. The method of claim 1, wherein the step of producing the metal ion acidic etching solution comprises: the substances in the step 4 are filtered by a second ultrasonic device (9) for 40-90s and a filtering system (1) with the pore diameter of 0.4-0.9 mu m.