CN112481052B

CN112481052B - Gold foil electrode cleaning agent and preparation method thereof

Info

Publication number: CN112481052B
Application number: CN202110065744.1A
Authority: CN
Inventors: 刘鸣; 孙宇亮; 刘利娟; 陆朝霞
Original assignee: Suzhou Jimcel Electronic New Material Co ltd
Current assignee: Suzhou Jimcel Electronic New Material Co ltd
Priority date: 2021-01-19
Filing date: 2021-01-19
Publication date: 2022-03-18
Anticipated expiration: 2041-01-19
Also published as: CN112481052A

Abstract

The invention discloses a novel gold foil electrode cleaning agent and a preparation method thereof, and belongs to the technical field of cleaning agents. The gold foil electrode cleaning agent comprises the following components in percentage by mass: 5-10% of glycolic acid, 1-5% of citric acid, 1-2% of formic acid, 1-10% of scale inhibitor, 0.5-1% of corrosion inhibitor and the balance of water. The components of the cleaning agent are selected and adjusted in a targeted manner, the glass powder deposited on the surface of the gold foil electrode has a strong dispersing and suspending effect, the cleaning equipment is simple, the cleaning time is short, and the existing electrophoretic glass passivation production process can be well met. In addition, through research on various surfactants and cleaning aids, the compound of the surfactants in a specific ratio has excellent penetration and dispersion on the deposit on the surface of the electrode.

Description

Gold foil electrode cleaning agent and preparation method thereof

Technical Field

The invention belongs to the technical field of cleaning agents, and particularly relates to a novel gold foil electrode cleaning agent and a preparation method thereof.

Background

The surface passivation technology is an important process link in the manufacturing process of a semiconductor device and has important influence on the electrical characteristics and reliability of the device. In the traditional semiconductor separation device products, the main semiconductor product surface passivation technology adopts silicon dioxide, silicon nitride, polyimide glue, white glue, glass and the like. As the glass as the passivation layer has the advantages of low cost and high reliability, the glass gradually replaces white glue, polyimide glue and the like, so that the glass becomes a mainstream material of the passivation layer on the surface of a semiconductor product. With the development of semiconductor technology, the demand for passivation of semiconductor surfaces is higher and higher.

In the prior art, a glass passivated silicon diode (GPP) chip made of special glass for semiconductor passivation is an ideal semiconductor passivation material. The electrophoretic glass passivation method is to prepare glass powder and organic solvents (isopropanol and ethyl acetate) into suspension, and add proper amount of activator and cellulose acetate into the suspension. Under the action of the direct current electric field, the glass particles with negative electricity move towards the direction of the silicon chip on the positive electrode and are deposited in the groove of the silicon chip.

Patent CN 106653600A discloses a GPP chip electrophoresis method manufacturing process, which comprises the steps of selecting manufacturing materials, cleaning a silicon wafer, pre-depositing phosphorus, diffusing boron, blasting sand on two sides to remove an oxidation layer, protecting passivation, passivating glass, rinsing and scribing, wherein the electrophoresis method is used for passivating glass so that the attachment surface of the glass is wider, the attachment is more uniform, and the quality of the GPP chip is improved.

However, in the electrophoresis process, the solid particles in the suspension can be deposited on the anode electrode, and the electrophoresis efficiency is continuously reduced along with the continuous deposition of the glass powder on the anode electrode, so the anode electrode must be taken out in time to clean the deposits on the surface of the anode electrode. At present, no special cleaning agent exists, and some similar electrode cleaning agents are used. Because the existing cleaning agent is not specific, and the glass powder deposited on the surface of the electrode is dense, the common electrode cleaning agent needs to be manually brushed after being soaked for a long time or ultrasonic cleaning equipment is used for removing the deposits on the surface of the electrode. For example, patent CN 108251231 a discloses an electrode cleaning agent and a preparation method thereof, wherein the electrode cleaning agent comprises: 1-5 parts of sodium citrate, 3-5 parts of sodium carbonate, 0.8-3 parts of sodium alginate, 4-8 parts of carboxymethyl cellulose, 0.5-3 parts of sodium dodecyl benzene sulfonate, 0.5-3 parts of succinic acid diester sulfonate, 1-6 parts of fatty acid methyl ester ethoxylate and 80-100 parts of water. However, the electrode cleaning agent only removes dirt attached to the surface of the electrode, and in addition, the electrophoretic deposition is fast in the electrophoretic glass passivation method, so that the electrode cleaning needs to be frequent, and if the cleaning needs a long time, the continuous production cannot be kept up with.

Therefore, the invention develops and designs a special electrode cleaning agent which can rapidly remove glass powder deposits on the surface of a gold foil electrode in an electrophoretic glass passivation method.

Disclosure of Invention

The invention aims to provide a novel gold foil electrode cleaning agent for cleaning glass powder deposits on the surface of an electrophoretic anode gold foil in a glass passivation process of a GPP chip electrophoresis method, aiming at solving the technical problems in the background art.

The invention also aims to provide a preparation method of the novel gold foil electrode cleaning agent.

The technical scheme adopted for realizing the aim of the invention is as follows:

a novel gold foil electrode cleaning agent comprises the following components in percentage by mass: 5-10% of glycolic acid, 1-5% of citric acid, 1-2% of formic acid, 1-10% of scale inhibitor, 0.5-1% of corrosion inhibitor and the balance of water.

Preferably, the scale inhibitor provided by the invention is selected from one or more of HEDP, EDTMPA or ATMP.

More preferably, the scale inhibitor is formed by mixing HEDP and EDTMPA according to the mass ratio of 1: 1.2.

Preferably, the corrosion inhibitor provided by the invention is selected from one or more of BTA, MBT and TTA.

More preferably, the corrosion inhibitor is composed of BTA and TTA mixed according to the mass ratio of 2: 1.

The technical scheme adopted for realizing the other purpose of the invention is as follows:

a preparation method of a novel gold foil electrode cleaning agent comprises the following steps:

step one, mixing glycolic acid, citric acid and formic acid according to a ratio and uniformly stirring;

step two, slowly adding the scale inhibitor into the mixed solution and uniformly stirring;

step three, slowly adding the corrosion inhibitor into the mixed solution and uniformly stirring;

and step four, adding water, and adjusting the pH value to 6-7 to obtain the electrode cleaning agent.

The invention has the advantages and beneficial effects that:

1. the components of the cleaning agent are selected and adjusted in a targeted manner, the glass powder deposited on the surface of the gold foil electrode has a strong dispersing and suspending effect, the cleaning equipment is simple, the cleaning time is short, and the existing electrophoretic glass passivation production process can be well met.

2. Through research on various different surfactants and cleaning aids, the compound of the surfactants in a certain specific ratio is found to have excellent penetration and dispersion on the deposits on the surface of the electrode, so the components and the weight percentage of the cleaning agent are finally determined, wherein the cleaning agent comprises the scale inhibitor HEDP and EDTMPA which are compounded according to the mass ratio of 1:1.2, and the corrosion inhibitor BTA and TTA which are compounded according to the mass ratio of 2:1, and has a certain synergistic effect on the cleaning effect on the deposits on the surface of the electrode.

3. The cleaning agent has good removing power for glass powder sediment on the surface of the gold foil electrode, and when the cleaning agent is used, the electrode is only required to be soaked in the cleaning agent for a short time and is washed with clean water after being taken out.

Detailed Description

The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.

Example 1:

1) mixing 5% of glycolic acid, 5% of citric acid and 1.5% of formic acid according to the proportion, and uniformly stirring;

2) slowly adding 10% of scale inhibitor into the mixed solution and uniformly stirring;

3) slowly adding 1% of corrosion inhibitor into the mixed solution and uniformly stirring, wherein the scale inhibitor is HEDP and EDTMPA mixed according to the mass ratio of 1:1.2, and the corrosion inhibitor is BTA and TTA mixed according to the mass ratio of 2: 1;

4) adding water, and adjusting the pH value to 6 to obtain the novel gold foil electrode cleaning agent.

Example 2:

1) mixing 10% of glycolic acid, 1% of citric acid and 2% of formic acid according to the proportion, and uniformly stirring;

2) slowly adding 6 percent of scale inhibitor into the mixed solution and uniformly stirring;

3) slowly adding 0.8% of corrosion inhibitor into the mixed solution and uniformly stirring, wherein the scale inhibitor is HEDP and EDTMPA mixed according to the mass ratio of 1:1.2, and the corrosion inhibitor is BTA and TTA mixed according to the mass ratio of 2: 1;

4) adding water, and adjusting the pH value to 6.5 to obtain the novel gold foil electrode cleaning agent.

Example 3:

1) mixing 8% of glycolic acid, 3% of citric acid and 1% of formic acid according to the proportion, and uniformly stirring;

2) slowly adding 1% of scale inhibitor into the mixed solution and uniformly stirring;

3) slowly adding 0.5% of corrosion inhibitor into the mixed solution and uniformly stirring, wherein the scale inhibitor is HEDP and EDTMPA mixed according to the mass ratio of 1:1.2, and the corrosion inhibitor is BTA and TTA mixed according to the mass ratio of 2: 1;

4) adding water, and adjusting the pH value to 7 to obtain the novel gold foil electrode cleaning agent.

The comparative tests were carried out at room temperature on the electrodes of the above examples, which were contaminated with glass powder deposits to the same extent by using the scale inhibitor alone and the corrosion inhibitor alone, respectively. The method is an electrode dipping method, electrodes with the same pollution degree of glass powder sediments are respectively put into the solution of the embodiment 1-3, the scale inhibitor and the corrosion inhibitor with the same mass, the soaking time is 2min, and the surface condition of each electrode is observed by a micrograph. The summary is given in Table 1 below:

TABLE 1

Example 1

Example 2

Example 3

Scale inhibitor HEDP

Scale inhibitor EDTMPA

Scale inhibitor ATMP

Corrosion inhibitor BTA

Corrosion inhibitor MBT

Corrosion inhibitor TTA

pH

6

6.5

7

-

Surface condition of the surface

Basically has no pollution

Has obvious pollution

Contamination with residual part

Without obvious change

Comparative example 1:

selecting a scale inhibitor which is a mixture of HEDP and EDTMPA according to the mass ratio of 1: 0.5; the corrosion inhibitor is prepared by mixing BTA and TTA according to the mass ratio of 3: 1. The rest is the same as example 1.

Comparative example 2:

selecting a scale inhibitor which is a mixture of HEDP and EDTMPA according to the mass ratio of 1: 2; the corrosion inhibitor is prepared by mixing BTA and TTA according to the mass ratio of 1:1. The rest is the same as example 2.

Comparative example 3:

selecting a scale inhibitor which is a mixture of HEDP and EDTMPA according to the mass ratio of 1: 3; the corrosion inhibitor is prepared by mixing BTA and TTA according to the mass ratio of 4: 1. The rest is the same as example 3.

Comparative tests were conducted at room temperature on electrodes having the same degree of contamination of glass frit deposits as in comparative examples 1 to 3 and examples 1 to 3. And (3) similarly, adopting an electrode dipping method, respectively putting the electrodes with the same pollution degree of the glass powder sediments into the solutions of the comparative examples 1-3, soaking for 5min, and observing the surface condition of each electrode by using a micrograph. The summary is given in Table 2 below:

TABLE 2

Example 1

Example 2

Example 3

Comparative example 1

Comparative example 2

Comparative example 3

pH

6

6.5

7

6

6.5

7

Surface condition of the surface

Basically has no pollution

Contamination with residual part

As can be seen from table 2, the scale inhibitors HEDP and EDTMPA in examples 1 to 3 of the present invention are compounded in a mass ratio of 1:1.2, and the corrosion inhibitors BTA and TTA are compounded in a mass ratio of 2:1, so that the electrode surface after the combined use is substantially free of pollution, and the effect is superior to the compound ratio of the scale inhibitors and corrosion inhibitors in comparative examples 1 to 3, which may be that the suitable concentration ratio can generate co-adsorption, and has a certain synergistic effect, and when the concentration is inappropriate, competitive adsorption occurs, resulting in poor effect.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims

1. The preparation method of the gold foil electrode cleaning agent is characterized by comprising the following steps:

adding water, and adjusting the pH value to 6-7 to obtain the electrode cleaning agent;

wherein, the mass percentage content of glycolic acid is 5-10%, citric acid is 1-5%, formic acid is 1-2%, scale inhibitor is 1-10%, corrosion inhibitor is 0.5-1%, and the balance is water;

the scale inhibitor is prepared by mixing HEDP and EDTMPA according to the mass ratio of 1: 1.2;

the corrosion inhibitor is prepared by mixing BTA and TTA according to the mass ratio of 2: 1.