CN114084872A - Stabilizer for electronic grade hydrogen peroxide solution and application - Google Patents
Stabilizer for electronic grade hydrogen peroxide solution and application Download PDFInfo
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- CN114084872A CN114084872A CN202111464171.6A CN202111464171A CN114084872A CN 114084872 A CN114084872 A CN 114084872A CN 202111464171 A CN202111464171 A CN 202111464171A CN 114084872 A CN114084872 A CN 114084872A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/037—Stabilisation by additives
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Abstract
The invention discloses a stabilizer of an electronic grade hydrogen peroxide solution and application thereof. The chelating or complexing organic phosphonic acid (or salt thereof) solution which is subjected to purification treatment is used as a main component, and only a trace amount of stabilizer is added into the ultra-clean high-purity hydrogen peroxide, so that the main effect of the hydrogen peroxide is not influenced, impurities are hardly introduced, the stability of the hydrogen peroxide is obviously enhanced, and the using effect of the hydrogen peroxide is better and obvious. Therefore, the application of the hydrogen peroxide in the electronic industry is more stable, and the yield, the electrical property and the reliability of electronic products are more stable. And the preparation process of the stabilizer is simple, is suitable for industrial production, and has good economic benefit.
Description
Technical Field
The invention belongs to the technical field of chemical stabilizers, and particularly relates to a stabilizer for an electronic grade hydrogen peroxide solution and application thereof.
Background
The electronic grade hydrogen peroxide water solution is one of the essential key chemical materials in the fine machining and making process of electronic technology, and is mainly used as cleaning agent, corrosive agent and photoresist remover for semiconductor wafer, high grade insulating layer in electronic industry, and removing inorganic impurity from electroplating solution, and the treatment of copper, copper alloy, gallium and germanium as semiconductor material, kinescope making process, etc. and its purity has very important influence on the yield, electric performance and reliability of integrated circuit.
Because the ultra-clean high-purity electronic grade hydrogen peroxide has low stability and is generally compounded with other electronic chemicals to form a working solution for use, more importantly, impurities such as metal ions, organic matters, particles and the like are inevitably mixed in the use process, so that the hydrogen peroxide becomes more unstable, and a stabilizer which can increase the stability and does not introduce the impurities as much as possible needs to be added.
At present, hydrogen peroxide stabilizers in the market mainly comprise inorganic phosphoric acid, magnesium salt, sodium stannate or organic phosphorus stabilizers and the like. The stabilizer partially solves the problems, but does not completely solve the problems, for example, the stabilizer such as inorganic phosphoric acid, magnesium salt, sodium stannate and the like is added into hydrogen peroxide and is widely applied to food-grade hydrogen peroxide or disinfectant hydrogen peroxide, impurities are inevitably introduced by adding the stabilizer, or the content of nonvolatile matters of a product exceeds the standard, a small amount of the stabilizer is added, the stabilizer can play a stabilizing role in the existence of single hydrogen peroxide, and once the hydrogen peroxide and other electronic chemicals are applied to links such as a cleaning agent, a corrosive agent and the like of a semiconductor crystal wafer together, the stability of the hydrogen peroxide is obviously reduced. The organic phosphine stabilizer belongs to a chelating or complexing stabilizer, has better effect than other inorganic stabilizers, and the main effect of the hydrogen peroxide cannot be influenced as long as a trace amount of organic phosphonic acid (or salts thereof) is added into the ultra-clean high-purity hydrogen peroxide, but the organic phosphonic acid (or salts thereof) which can be obtained in the market at present are industrial-grade products, and the purity of the organic phosphonic acid (or salts thereof) cannot reach the standard of the ultra-clean high-purity electronic-grade hydrogen peroxide stabilizer.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to design and provide a stabilizer for an electronic grade hydrogen peroxide solution and an application technical scheme. The stabilizer can ensure the stability of a single hydrogen peroxide solution or the compounding use of hydrogen peroxide and other electronic chemicals. Only a trace amount of stabilizer is added into the ultra-clean high-purity hydrogen peroxide, so that the main effect of the hydrogen peroxide is not influenced, impurities are hardly introduced, the stability of the hydrogen peroxide is obviously enhanced, and the using effect of the hydrogen peroxide is more obvious. And the preparation process of the stabilizer is simple, is suitable for industrial production, and has good economic benefit. The method is realized by the following technical scheme:
the stabilizer for the electronic grade hydrogen peroxide solution is a solution consisting of organic phosphonic acid or salts thereof and excess water, wherein the organic phosphonic acid or salts thereof are substances having chelation or complexation effects on metal ions in the hydrogen peroxide solution.
Further, the weight ratio of the organic phosphonic acid or the salt thereof to the excess water in the stabilizer is 1-3: 1-2.
Further, the organic phosphonic acid or its salt mainly includes nitrilotrimethylene phosphonic acid, 1, 2-propylenediaminetetramethylene phosphonic acid, 2-hydroxyphosphonoacetic acid, diethylenetriaminepentamethylene phosphonic acid, hydroxyethylidene diphosphonic acid, 1-hydroxyethylidene diphosphonic acid.
Further, the stabilizer can be a solution consisting of a single organic phosphonic acid or a salt thereof, or a mixed solution consisting of two or more organic phosphonic acids or salts thereof; the content of the electronic grade hydrogen peroxide solution is 25-50%.
The stabilizer is applied to an electronic grade hydrogen peroxide solution.
Further, the stabilizer is added into the electronic grade hydrogen peroxide solution to be directly mixed under a clean environment, and the adding amount of the stabilizer is that the concentration range of the organic phosphonic acid or the salt thereof is 1-10 mg/L.
Further, the stabilizer is added in an amount such that the concentration of the organophosphonic acid or salt thereof is in the range of 1 to 5 mg/L.
Further, before the stabilizer is added into the electronic grade hydrogen peroxide solution, pretreatment is carried out, wherein the pretreatment refers to that organic phosphonic acid or salt solution thereof with certain concentration is prepared in a clean room and is purified by resin.
Wherein the purification treatment specifically comprises the steps of sequentially passing the organic phosphonic acid or salt solution thereof through one or more groups of resin purification systems at the flow rate of 1-10 times of the resin volume per hour, then filtering through one or more groups of filter element circulating systems, and controlling the temperature of the stabilizer to 5-25 ℃ to enter the resin purification systems, wherein the material of the contact part of the purification device and the stabilizer is PTFE, FEP or PFA.
Further, the flow rate of the organic phosphonic acid or salt solution thereof is 2 to 5 times the resin volume per hour, in each group of resin purification systems: the cation exchange resin, the mixed resin and the anion exchange resin are randomly combined, wherein the cation and anion exchange resins are selected from polishing resin, electronic grade resin or nuclear grade resin.
The chelating or complexing organic phosphonic acid (or salt thereof) solution which is subjected to purification treatment is used as a main component, and only a trace amount of stabilizer is added into the ultra-clean high-purity hydrogen peroxide, so that the main effect of the hydrogen peroxide is not influenced, impurities are hardly introduced, the stability of the hydrogen peroxide is obviously enhanced, and the using effect of the hydrogen peroxide is better and obvious. Therefore, the application of the hydrogen peroxide in the electronic industry is more stable, and the yield, the electrical property and the reliability of electronic products are more stable. And the preparation process of the stabilizer is simple, is suitable for industrial production, and has good economic benefit.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A stabilizer for an electronic grade hydrogen peroxide solution is composed of the following raw materials in percentage by weight: 20% of nitrilotrimethylene phosphonic acid, 20% of 1, 2-propane diamine tetramethylene phosphonic acid, 20% of 1-hydroxyethylidene diphosphonic acid and 40% of ultrapure water.
The preparation method comprises the following steps: sequentially adding nitrilotrimethylene phosphonic acid, 1, 2-propane diamine tetramethylene phosphonic acid and 1-hydroxyethylidene diphosphonic acid into ultrapure water to meet the proportioning requirement, and stirring for 2 hours to fully dissolve and uniformly mix the components. And then purifying the stabilizer by a group of electronic grade cation and anion resins at a flow rate of 3 times of the volume of the resin per hour to obtain the electronic grade hydrogen peroxide stabilizer.
The stabilizer was mixed directly with 31.52% electronic grade hydrogen peroxide in a clean room at room temperature, the concentration of the organic phosphonic acid (or salt thereof) in the hydrogen peroxide solution was 3 mg/L. And preparing a compound solution according to the proportion of 1 part of ammonia water, 2 parts of hydrogen peroxide and 7 parts of ultrapure water, and carrying out 2-hour 80 ℃ constant-temperature water bath treatment. The hydrogen peroxide solution without the stabilizer and the hydrogen peroxide without the purified stabilizer are used as control groups. The results are shown in Table 1.
Table 1: change condition of each index of single hydrogen peroxide and compound solution
Example 2
A stabilizer for an electronic grade hydrogen peroxide solution is composed of the following raw materials in percentage by weight: 60% of hydroxyethylidene diphosphonic acid and 40% of ultrapure water.
The preparation method comprises the following steps: adding hydroxyethylidene diphosphonic acid into ultrapure water to the proportioning requirement, and stirring for 2 hours to fully dissolve and uniformly mix the components. And then purifying the stabilizer by a group of electronic grade cation and anion resins and a group of polishing mixed bed resins at a flow rate of 5 times of the volume of the resin per hour to obtain the electronic grade hydrogen peroxide stabilizer.
The stabilizer was mixed directly with 35.46% electronic grade hydrogen peroxide in a clean room at room temperature, the concentration of the organic phosphonic acid (or salt thereof) in the hydrogen peroxide solution was 5 mg/L. And preparing a compound solution according to the proportion of 1 part of ammonia water, 2 parts of hydrogen peroxide and 7 parts of ultrapure water, and carrying out 3-hour constant-temperature water bath treatment at 70 ℃. The hydrogen peroxide solution without the stabilizer and the hydrogen peroxide without the purified stabilizer are used as control groups. The results are shown in Table 2.
TABLE 2 Change of the indexes of the single hydrogen peroxide and the compounded solution
Example 3
A stabilizer for an electronic grade hydrogen peroxide solution is composed of the following raw materials in percentage by weight: 10% of 2-hydroxyphosphonoacetic acid, 10% of diethylenetriamine pentamethylene phosphonic acid, 30% of hydroxyethylidene diphosphonic acid and 50% of ultrapure water.
The preparation method comprises the following steps: sequentially adding 2-hydroxyphosphonoacetic acid, diethylenetriamine pentamethylene phosphonic acid and hydroxyethylidene diphosphonic acid into ultrapure water to meet the proportioning requirement, and stirring for 2 hours to fully dissolve and uniformly mix the components. And then purifying the stabilizer by passing through a group of electronic grade cation and anion resins and a group of nuclear grade cation and anion resins at a flow rate of 2 times of the volume of the resin per hour to obtain the electronic grade hydrogen peroxide stabilizer.
The stabilizer was mixed directly with 31.36% electronic grade hydrogen peroxide in a clean room at room temperature, the concentration of the organic phosphonic acid (or salt thereof) in the hydrogen peroxide solution was 2 mg/L. And preparing a compound solution according to the proportion of 1 part of ammonia water, 2 parts of hydrogen peroxide and 7 parts of ultrapure water, and carrying out 5-hour constant-temperature water bath treatment at 65 ℃. The hydrogen peroxide solution without the stabilizer and the hydrogen peroxide without the purified stabilizer are used as control groups. The results are shown in Table 3.
TABLE 3 Change of the indexes of the single hydrogen peroxide and the compounded solution
Claims (10)
1. The stabilizer for electronic grade hydrogen peroxide solution is a solution composed of organic phosphonic acid or its salt and excess water, wherein the organic phosphonic acid or its salt is a substance having chelating or complexing action on metal ions in the hydrogen peroxide solution.
2. The stabilizer for an electronic grade hydrogen peroxide solution according to claim 1, wherein the weight ratio of the organic phosphonic acid or the salt thereof to the excess water in the stabilizer is 1-3: 1-2.
3. The stabilizer for an electronic grade hydrogen peroxide solution according to claim 1, wherein the organic phosphonic acid or its salt mainly comprises nitrilotrimethylene phosphonic acid, 1, 2-propanediamine tetramethylene phosphonic acid, 2-hydroxyphosphonoacetic acid, diethylenetriamine pentamethylene phosphonic acid, hydroxyethylidene diphosphonic acid, 1-hydroxyethylidene diphosphonic acid.
4. The stabilizer for electronic grade hydrogen peroxide solution according to claim 1, wherein the stabilizer is a solution of a single organic phosphonic acid or a salt thereof, or a mixed solution of two or more organic phosphonic acids or salts thereof; the content of the electronic grade hydrogen peroxide solution is 25-50%.
5. Use of a stabilizer according to any one of claims 1 to 4 in an electronic grade hydrogen peroxide solution.
6. The use according to claim 5, wherein the stabilizer is added to the electronic grade hydrogen peroxide solution in a clean environment and mixed directly, and the adding amount of the stabilizer is that the concentration of the organic phosphonic acid or the salt thereof is in the range of 1-10 mg/L.
7. The use according to claim 6, wherein the stabilizer is added in a concentration of the organophosphonic acid or salt thereof in the range of 1 to 5 mg/L.
8. Use according to claim 6, wherein the stabilizer is pre-treated by purifying the solution of the organic phosphonic acid or salt thereof with a resin in a clean room before adding it to the solution of electronic grade hydrogen peroxide.
9. The use of claim 8, wherein the solution of organic phosphonic acid or its salt is passed through one or more resin purification systems sequentially at a flow rate of 1-10 times the resin volume/hour, and then filtered through one or more filter element circulation systems, and the temperature of the stabilizer is controlled to 5-25 ℃ to enter the resin purification system, wherein the contact part of the purification device and the stabilizer is selected from PTFE, FEP or PFA.
10. The use according to claim 9, wherein the flow rate of the solution of the organophosphonic acid or salt thereof is 2 to 5 resin volumes per hour, and wherein in each resin purification system: the cation exchange resin, the mixed resin and the anion exchange resin are randomly combined, wherein the cation and anion exchange resins are selected from polishing resin, electronic grade resin or nuclear grade resin.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111464171.6A CN114084872A (en) | 2021-12-03 | 2021-12-03 | Stabilizer for electronic grade hydrogen peroxide solution and application |
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| CN202111464171.6A CN114084872A (en) | 2021-12-03 | 2021-12-03 | Stabilizer for electronic grade hydrogen peroxide solution and application |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5290361A (en) * | 1991-01-24 | 1994-03-01 | Wako Pure Chemical Industries, Ltd. | Surface treating cleaning method |
| US20020127281A1 (en) * | 2000-09-28 | 2002-09-12 | Fu-Pao Tsao | Stabilized hyrogen peroxide solutions |
| CN102295274A (en) * | 2011-06-16 | 2011-12-28 | 天津运盛化学品有限公司 | Hydrogen peroxide stabilizing agent |
| CN103896217A (en) * | 2012-12-29 | 2014-07-02 | 新煤化工设计院（上海）有限公司 | Stabilizer of hydrogen peroxide |
| CN106185830A (en) * | 2016-07-01 | 2016-12-07 | 苏州博洋化学股份有限公司 | A kind of hydrogen peroxide stabilizer and using method thereof |
| CN113371683A (en) * | 2020-12-16 | 2021-09-10 | 惠州市宙邦化工有限公司 | Production method of electronic-grade hydrogen peroxide |
-
2021
- 2021-12-03 CN CN202111464171.6A patent/CN114084872A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5290361A (en) * | 1991-01-24 | 1994-03-01 | Wako Pure Chemical Industries, Ltd. | Surface treating cleaning method |
| US20020127281A1 (en) * | 2000-09-28 | 2002-09-12 | Fu-Pao Tsao | Stabilized hyrogen peroxide solutions |
| CN102295274A (en) * | 2011-06-16 | 2011-12-28 | 天津运盛化学品有限公司 | Hydrogen peroxide stabilizing agent |
| CN103896217A (en) * | 2012-12-29 | 2014-07-02 | 新煤化工设计院（上海）有限公司 | Stabilizer of hydrogen peroxide |
| CN106185830A (en) * | 2016-07-01 | 2016-12-07 | 苏州博洋化学股份有限公司 | A kind of hydrogen peroxide stabilizer and using method thereof |
| CN113371683A (en) * | 2020-12-16 | 2021-09-10 | 惠州市宙邦化工有限公司 | Production method of electronic-grade hydrogen peroxide |
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