CN114875405A - Hydrogen peroxide system metal etching composition and preparation method thereof - Google Patents
Hydrogen peroxide system metal etching composition and preparation method thereof Download PDFInfo
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- CN114875405A CN114875405A CN202210507575.7A CN202210507575A CN114875405A CN 114875405 A CN114875405 A CN 114875405A CN 202210507575 A CN202210507575 A CN 202210507575A CN 114875405 A CN114875405 A CN 114875405A
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- acid
- hydrogen peroxide
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
Abstract
The invention relates to the field of IPC classified C23F, in particular to a hydrogen peroxide aqueous metal etching composition and a preparation method thereof. The composition is formed by mixing a main agent and an auxiliary agent; the main agent comprises the following components: hydrogen peroxide, organic acid, organic base, stabilizer, azole and deionized water; the adjuvant comprises the following components: organic acid, organic base, stabilizer, azole and deionized water. The composition has high copper ion loading capacity, avoids corrosivity on an etching object because the composition does not contain strong acidic substances such as hydrofluoric acid, nitric acid and the like, has a proper angle on an etched metal film layer, does not have chamfer, has low line width loss (less than or equal to 0.5 mu m), has the highest copper loading capacity of more than or equal to 14000ppm, and is suitable for popularization in the field of etching liquid.
Description
Technical Field
The invention relates to the field of IPC classified C23F, in particular to a hydrogen peroxide aqueous metal etching composition and a preparation method thereof.
Background
Metal etching is a technique for removing surface metal by chemically reacting or physically rubbing a metal material using two methods, wet etching and dry etching. With the continuous improvement of living standard and scientific technology level, the requirement of the product on metal etching is higher and higher. For example, ultra-high definition display products require that metal plate wires are densely arranged and can meet electrical requirements, so that the etched metal plate cannot be too low in angle after etching, cannot have a chamfer, has high copper ion loading capacity, and requires that etching liquid cannot have high corrosivity and cannot influence product quality.
The prior art (CN202010652548.X) provides a metal etching solution, which mainly adopts hydrogen peroxide, nitric acid, hydrofluoric acid and the like as main raw materials of the etching solution, and the etching solution prepared by the metal etching solution is claimed to be capable of etching various metal films and has excellent etching efficiency, but because the etching solution adopts strong corrosive and oxidizing substances such as hydrofluoric acid, nitric acid and the like, the etching solution cannot play a good role in the etching process of ultra-high-definition products, and the yield of the products is easily and greatly reduced.
Accordingly, the present application provides a hydrogen peroxide-based metal etching composition to solve the above problems.
Disclosure of Invention
In order to solve the above problems, the present invention provides, in a first aspect, a hydrogen peroxide-based metal etching composition, which comprises a main agent and an auxiliary agent in admixture; the main agent comprises the following components: hydrogen peroxide, organic acid, organic base, stabilizer, azole and deionized water; the adjuvant comprises the following components: organic acid, organic base, stabilizer, azole and deionized water.
As a preferable scheme, the mass ratio of the main agent to the auxiliary agent is 100: 0.5-1.5.
As a preferable scheme, the main agent comprises the following components in percentage by mass: 5-30% of hydrogen peroxide, 1-15% of organic acid, 0.1-15% of organic base, 0.01-1% of stabilizer, 0.01-1% of azole and the balance of deionized water; the auxiliary agent comprises the following components in percentage by mass: 10-30% of organic acid, 10-30% of organic base, 0.01-1% of stabilizer, 0.01-1% of azole and the balance of deionized water.
As a preferable scheme, the main agent comprises the following components in percentage by mass: 6-15% of hydrogen peroxide, 1-10% of organic acid, 0.2-10% of organic base, 0.05-0.5% of stabilizer, 0.01-0.3% of azole and the balance of deionized water.
As a preferable scheme, the adjuvant comprises the following components in percentage by mass: 20-30% of organic acid, 15-25% of organic base, 0.05-0.5% of stabilizer, 0.01-0.5% of azole and the balance of deionized water.
Preferably, the mass ratio of the hydrogen peroxide to the organic acid and the organic base in the main agent is 8-12: 3-5: 3 to 4.
In a preferred embodiment, the organic acid is at least one of iminodiacetic acid, carbamic acid, glycine, oxalic acid, malonic acid, succinic acid, malic acid, citric acid, triammonium triacetate, tartaric acid, malonic acid, and sulfamic acid.
As a preferred scheme, the organic base has the structure
Wherein R1, R2 and R3 are straight-chain or branched-chain alkyl groups and are mutually independent; the organic base does not include the following structure:
wherein R1, R2 and R3 are respectively independent C1-C5 straight chain or branched chain alkyl.
In a preferred embodiment, the organic base is at least one of tetramethylammonium hydroxide, ammonia water, methylamine, ethylenediamine, propylenediamine, isopropanolamine, tris (hydroxymethyl) aminomethane, triaminoethylpropylamine, diethylaminopropylamine, triethanolamine, diethanolamine, and triethylamine.
In a preferred embodiment, the stabilizer is phenylurea and/or p-hydroxybenzene sulfonic acid.
As a preferred embodiment, the stabilizer is phenylurea.
As a preferable scheme, the azole is at least one of 3-aminotriazole, 5-aminotriazole and triazole.
In a preferable scheme, the azole is 5-aminotetrazole.
As a preferred embodiment, the organic acid is a mixture of malonic acid and malic acid; the mass ratio of malonic acid to malic acid in the main agent is 2-3: 1.
As a preferable scheme, the mass ratio of the malonic acid to the malic acid in the main agent is 2: 1.
As a preferable scheme, the mass ratio of the malonic acid to the malic acid in the auxiliary agent is 18: 7.5.
As a preferred embodiment, the organic base is a mixture of diethylaminopropylamine and isopropanolamine; the mass ratio of diethylaminopropylamine to isopropanolamine in the main agent is 0.5-1: 2.2 to 2.7.
As a preferable scheme, the mass ratio of diethylaminopropylamine to isopropanolamine in the main agent is 0.8: 2.5.
as a preferable scheme, the mass ratio of diethylaminopropylamine to isopropanolamine in the adjuvant is 4.6-5.2: 13.5 to 16.
In the application, the proportion of the organic base and the organic acid mixture in the main agent and the auxiliary agent is selected and the mixture is compounded with hydrogen peroxide, so that the etching quality and the etching efficiency of the etching solution are effectively improved, and the stability of the etching solution is further improved. The applicant believes that: in this application, the specific organic acid and the organic base raw materials of adoption not only can play good metal and get rid of effect and copper ion complex ability at the in-process synergism of sculpture, can also effectual stable pH environment, chelate metal ion, weaken metal ion to the catalytic decomposition effect of hydrogen peroxide, effectively improve whole system stability to cooperate the azole in this application can adjust out good rete etching rate.
The second aspect of the invention provides a preparation method of the hydrogen peroxide-based metal etching composition, which comprises the following steps: weighing the raw materials required by the main agent and the auxiliary agent, respectively mixing and stirring uniformly in a stirring container, taking out and subpackaging to obtain the compound preparation.
Has the advantages that:
1. the hydrogen peroxide aqueous metal etching liquid composition provided by the application can have higher copper ion loading capacity during metal etching, meanwhile, because the hydrogen peroxide aqueous metal etching liquid composition does not contain strong acidic substances such as hydrofluoric acid and nitric acid, the corrosivity to an etching object is avoided, an etched metal film layer has a proper angle, no chamfer exists, the line width loss is low (less than or equal to 0.5 mu m), and the highest copper loading capacity is more than or equal to 14000 ppm; this enables the etched metal of the composition of the present application to be effectively used in ultra high definition display products.
2. According to the hydrogen peroxide aqueous metal etching liquid composition, the proportion of organic base and organic acid mixture in the main agent and the auxiliary agent is selected, and the hydrogen peroxide aqueous metal etching liquid composition is compounded with hydrogen peroxide, so that the etching quality and the etching efficiency of the etching liquid are effectively improved, and the stability of the etching liquid is further improved.
Detailed Description
Example 1
Example 1 in a first aspect, there is provided a hydrogen peroxide-based metal etching composition comprising a main agent and an auxiliary agent in admixture;
the main agent comprises the following components in percentage by mass: 10% of hydrogen peroxide, 4.5% of organic acid (3% of malonic acid and 1.5% of malic acid), 3.3% of organic base (0.8% of diethylaminopropylamine and 2.5% of isopropanolamine), 0.2% of stabilizer (phenylurea), 0.03% of azole (5-aminotetrazole) and the balance of deionized water.
The auxiliary agent comprises the following components in percentage by mass: 25.5% of organic acid (18% of malonic acid, 7.5% of malic acid), 18.8% of organic base (4.8% of diethylaminopropylamine, 14% of isopropanolamine), 0.3% of stabilizer (phenylurea), 0.16% of azole (5-aminotetrazole) and the balance of deionized water.
The mass ratio of the main agent to the auxiliary agent is 100: 1.
In a second aspect of this embodiment, a method for preparing the above-mentioned hydrogen peroxide-based metal etching composition is provided, which includes the steps of: weighing the raw materials required by the main agent and the auxiliary agent, respectively mixing and stirring uniformly in a stirring container, taking out and subpackaging to obtain the compound preparation.
Example 2
Embodiment 2 in a first aspect, there is provided a hydrogen peroxide-based metal etching composition, which comprises a main agent and an auxiliary agent in admixture;
the main agent comprises the following components in percentage by mass: 10% of hydrogen peroxide, 4.5% of organic acid (3% of malonic acid and 1.5% of malic acid), 3.2% of organic base (0.5% of diethylaminopropylamine and 2.7% of isopropanolamine), 0.2% of stabilizer (phenylurea), 0.03% of azole (5-aminotetrazole) and the balance of deionized water.
The auxiliary agent comprises the following components in percentage by mass: 25.5% of organic acid (18% of malonic acid, 7.5% of malic acid), 21.2% of organic base (5.2% of diethylaminopropylamine, 16% of isopropanolamine), 0.3% of stabilizer (phenylurea), 0.16% of azole (5-aminotetrazole) and the balance of deionized water.
In a second aspect of this embodiment, a method for preparing the above-mentioned hydrogen peroxide-based metal etching composition is provided, which includes the steps of: weighing the raw materials required by the main agent and the auxiliary agent, respectively mixing and stirring uniformly in a stirring container, taking out and subpackaging to obtain the compound preparation.
Example 3
Embodiment 3 in a first aspect, a hydrogen peroxide-based aqueous metal etching composition is provided, which comprises a main agent and an auxiliary agent;
the main agent comprises the following components in percentage by mass: 10% of hydrogen peroxide, 4.5% of organic acid (3% of malonic acid and 1.5% of malic acid), 3.2% of organic base (1% of diethylaminopropylamine and 2.2% of isopropanolamine), 0.2% of stabilizer (phenylurea), 0.03% of azole (5-aminotetrazole) and the balance of deionized water.
The auxiliary agent comprises the following components in percentage by mass: 25.5% of organic acid (18% of malonic acid, 7.5% of malic acid), 18.1% of organic base (4.6% of diethylaminopropylamine, 13.5% of isopropanolamine), 0.3% of stabilizer (phenylurea), 0.16% of azole (5-aminotetrazole) and the balance of deionized water.
In a second aspect of this embodiment, a method for preparing the above-mentioned hydrogen peroxide-based metal etching composition is provided, which includes the steps of: weighing the raw materials required by the main agent and the auxiliary agent, respectively mixing and stirring uniformly in a stirring container, taking out and subpackaging to obtain the compound preparation.
Comparative example 1
The embodiment of this comparative example is the same as example 1 except that: in the main agent, the diethylaminopropylamine accounts for 0.1 percent, and the isopropanolamine accounts for 3 percent; in the adjuvant, diethylaminopropylamine was 1% and isopropanolamine was 17.6%.
Comparative example 2
The embodiment of this comparative example is the same as example 1 except that: in the main agent, diethylaminopropylamine accounts for 3 percent, and isopropanolamine accounts for 0.2 percent; in the adjuvant, diethylaminopropylamine was 4.9% and isopropanolamine was 3.7%.
Comparative example 3
The embodiment of this comparative example is the same as example 1 except that: in the main agent, diethylaminopropylamine accounts for 0 percent, and isopropanolamine accounts for 3.3 percent; in the adjuvant, diethylaminopropylamine was 0% and isopropanolamine was 17.2%.
Evaluation of Performance
And (3) testing an etching effect: copper film thickness (a): 4500; molybdenum niobium film thickness (a): 300, respectively; etching temperature (. degree. C.): 32, a first step of removing the first layer; etching time (sec): 120 to 145. The etched metal film was subjected to metal residue, chamfering, cracking, CD-loss (single side, μm), taper angle (°), maximum copper loading (ppm)
TABLE 1
Through the embodiment, the comparative example and the performance test, the hydrogen peroxide system metal etching composition provided by the invention has higher copper ion loading capacity, meanwhile, because the hydrogen peroxide system metal etching composition does not contain strong acidic substances such as hydrofluoric acid, nitric acid and the like, the corrosivity to an etching object is avoided, an etched metal film layer has a proper angle, no chamfer exists, the line width loss is low (less than or equal to 0.5 mu m), the highest copper loading capacity is more than or equal to 14000ppm, the hydrogen peroxide system metal etching composition is suitable for being popularized in the field of etching solutions, and the hydrogen peroxide system metal etching composition has a wide development prospect.
Claims (10)
1. A hydrogen peroxide-based metal etching composition characterized by: the composition is formed by mixing a main agent and an auxiliary agent; the main agent comprises the following components: hydrogen peroxide, organic acid, organic base, stabilizer, azole and deionized water; the adjuvant comprises the following components: organic acid, organic base, stabilizer, azole and deionized water.
2. The hydrogen peroxide-based metal etching composition according to claim 1, wherein: the main agent comprises the following components in percentage by mass: 5-30% of hydrogen peroxide, 1-15% of organic acid, 0.1-15% of organic base, 0.01-1% of stabilizer, 0.01-1% of azole and the balance of deionized water; the auxiliary agent comprises the following components in percentage by mass: 10-30% of organic acid, 10-30% of organic base, 0.01-1% of stabilizer, 0.01-1% of azole and the balance of deionized water.
3. The hydrogen peroxide-based metal etching composition according to any one of claims 1 to 2, wherein: the mass ratio of hydrogen peroxide to organic acid and organic base in the main agent is 8-12: 3-5: 3 to 4.
4. The hydrogen peroxide-based metal etching composition according to claim 3, wherein: the organic acid is at least one of iminodiacetic acid, carbamic acid, glycine, oxalic acid, malonic acid, succinic acid, malic acid, citric acid, triacetamine, tartaric acid, malonic acid and sulfamic acid.
5. The method of claim 4The hydrogen peroxide-based metal etching composition of (1), characterized in that: the organic base has the structure of
Wherein R1, R2 and R3 are straight-chain or branched-chain alkyl groups and are mutually independent; the organic base does not include the following structure:
wherein R1, R2 and R3 are respectively independent C1-C5 straight chain or branched chain alkyl.
6. The hydrogen peroxide-based metal etching composition according to claim 5, wherein: the stabilizer is phenylurea and/or p-hydroxybenzene sulfonic acid.
7. The hydrogen peroxide-based metal etching composition according to claim 6, wherein: the azole is at least one of 3-amino triazole, 5-amino tetrazole and triazole.
8. The hydrogen peroxide-based metal etching composition according to claim 7, wherein: the organic acid is a mixture of malonic acid and malic acid; the mass ratio of the malonic acid to the malic acid in the main agent is 2-3: 1.
9. The hydrogen peroxide-based metal etching composition according to claim 8, wherein: the organic base is a mixture of diethylaminopropylamine and isopropanolamine; the mass ratio of diethylaminopropylamine to isopropanolamine in the main agent is 0.5-1: 2.2 to 2.7.
10. A method for producing the aqueous hydrogen peroxide-based metal etching composition according to any one of claims 1 to 9, characterized in that: the method comprises the following steps: weighing the raw materials required by the main agent and the auxiliary agent, respectively mixing and stirring uniformly in a stirring container, taking out and subpackaging to obtain the compound preparation.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104611701A (en) * | 2013-11-01 | 2015-05-13 | 达兴材料股份有限公司 | Etching solution composition and etching method |
| CN107075693A (en) * | 2014-11-18 | 2017-08-18 | 关东化学株式会社 | Copper, molybdenum stacked film etchant, the engraving method using said composition and extend said composition life-span method |
| CN111663138A (en) * | 2020-07-08 | 2020-09-15 | 江苏和达电子科技有限公司 | Etching solution for copper-containing laminated film of liquid crystal panel and application thereof |
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- 2022-05-10 CN CN202210507575.7A patent/CN114875405A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104611701A (en) * | 2013-11-01 | 2015-05-13 | 达兴材料股份有限公司 | Etching solution composition and etching method |
| CN107075693A (en) * | 2014-11-18 | 2017-08-18 | 关东化学株式会社 | Copper, molybdenum stacked film etchant, the engraving method using said composition and extend said composition life-span method |
| CN111663138A (en) * | 2020-07-08 | 2020-09-15 | 江苏和达电子科技有限公司 | Etching solution for copper-containing laminated film of liquid crystal panel and application thereof |
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