Preparation method of hydroxylamine compound cleaning fluid

Abstract

The invention discloses a preparation method of a hydroxylamine compound cleaning solution. The preparation method of the hydroxylamine compound cleaning fluid comprises the following step: mixing the components of the hydroxylamine compound cleaning fluid. The hydroxylamine compound cleaning solution is prepared from the following components in percentage by mass: 1 to 30 percent of a hydroxylamine compound, 1 to 5 percent of a corrosion inhibitor, 0.1 to 5 percent of a chelating agent, 0.01 to 5 percent of a nonionic surfactant and 1 to 50 percent of a water-soluble organic solvent and water. The sum of the mass fractions of the components is 100%. The hydroxylamine compound cleaning fluid has a good cleaning effect, is low in corrosivity, is safe and environment-friendly, and has a good application prospect.

Description

Technical Field

[0001] The present invention relates to a preparation method of a hydroxylamine compound cleaning solution. Background Art

[0002] In the development of semiconductor integrated circuits, large scale, high density, and miniaturization have become the development trends. In the manufacturing process thereof, the coating, exposure, development, and etching of the photoresist layer are necessary process steps for the pattern manufacturing of components. At the end of patterning (i.e., after the coating, imaging, ion implantation, and dry etching of the photoresist layer), before the next process step, the residues of the photoresist layer material need to be completely removed. During the dry etching or ion implantation process, ion bombardment hardens the surface layer of the photoresist, forming a hard, carbonized outer shell, which prevents the cleaning solution from cleaning the underlying main photoresist. The commonly used cleaning method involves an ashing process of oxygen plasma to penetrate the above hard outer shell and remove the photoresist.

[0003] The residues after aluminum process chip etching coexist with dielectric etching. With the upgrade of technology, different material types are applied to the aluminum process. Hydroxylamine can effectively remove etching residues without damaging the dielectric layer. Currently, the removal of aluminum process residues mainly uses a hydroxylamine cleaning solution. However, due to the use of hydroxylamine, the source of the cleaning agent raw materials is fixed, and there is an explosion risk during the storage and use of hydroxylamine. Therefore, using a hydroxylamine substitute to develop a low-cost, high-efficiency, and more compatible aqueous cleaning agent is the direction of improvement and optimization in this field. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the existing fixed source of cleaning agent raw materials and the explosion risk of hydroxylamine during storage and use. Therefore, a preparation method of a hydroxylamine compound cleaning solution is provided. The hydroxylamine compound cleaning solution obtained by the preparation method of the present invention has one or more of the following effect advantages compared with the traditional hydroxylamine cleaning solution: low cost, high efficiency, and stronger compatibility.

[0005] The present invention provides a preparation method of a hydroxylamine compound cleaning solution, which includes the following steps: mixing the components of the hydroxylamine compound cleaning solution; the hydroxylamine compound cleaning solution includes the following components by mass fraction: 1-30% of a hydroxylamine compound, 1-5% of a resist, 0.1-5% of a chelating agent, 0.01-5% of a nonionic surfactant, 1-50% of a water-soluble organic solvent, and water; the sum of the mass fractions of each component is 100%, and the mass fraction is the percentage of the mass of each component in the total mass of each component.

[0006] In certain preferred embodiments of the present invention, some components and mass fractions in the preparation method of the hydroxylamine compound cleaning solution are defined as follows. The components and mass fractions not mentioned are the same as those described in any embodiment of the present invention (abbreviated as "in some embodiments").

[0007] In some embodiments, the hydroxylamine compound is selected from one or more of N-methylhydroxylamine, N-ethylhydroxylamine, and N,N-diethylhydroxylamine; preferably N-methylhydroxylamine and / or N,N-diethylhydroxylamine.

[0008] In some embodiments, the resist is selected from one or more of catechol, pyrogallol, alkyl gallate, and alkyl catechol; preferably catechol.

[0009] In some embodiments, the chelating agent is an organic acid, preferably selected from one or more of amino acids, ethylenediaminetetraacetic acid (EDTA), lactic acid, benzoic acid, glycolic acid, malonic acid, maleic acid, salicylic acid, glyceric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid, malic acid, methanesulfonic acid, ethanesulfonic acid, hydroxyethanesulfonic acid, tartaric acid, citric acid, citrulline, gallic acid, and gallic acid; preferably ethylenediaminetetraacetic acid.

[0010] In some embodiments, the nonionic surfactant is an EO-PO polymer, preferably selected from one or more of EO-PO polymer L42, EO-PO polymer L43, and EO-PO polymer L44; preferably EO-PO polymer L42.

[0011] In some embodiments, the water-soluble organic solvent can be a conventional solvent in the art, preferably a sulfone solvent and / or an alcohol solvent, more preferably dimethyl sulfoxide and / or triethylene glycol.

[0012] In some embodiments, the water is selected from one or more of deionized water, distilled water, and ultrapure water, such as deionized water.

[0013] In some embodiments, the mass fraction of the hydroxylamine compound is preferably 1-30%, more preferably 2% to 25%; for example, 5%, 10%, 15%, or 20%.

[0014] In some embodiments, the mass fraction of the resist is preferably 1-5%, more preferably 1% to 4%; for example, 2%.

[0015] In some embodiments, the mass fraction of the chelating agent is preferably 0.1-5%, more preferably 0.1% to 1%; for example, 0.5%.

[0016] In some embodiments, the mass fraction of the non-ionic surfactant is preferably 0.01-5%, more preferably 0.5%-4%; for example, 1%.

[0017] In some embodiments, the mass fraction of the water-soluble organic solvent is preferably 1-50%, more preferably 10%-40%; for example, 25%.

[0018] In some embodiments, the hydroxylamine compound cleaning solution comprises the following components in mass fractions: 5%-20% of hydroxylamine compounds, 1.5%-2.5% of resist, 0.2%-0.8% of chelating agent, 0.5%-1.5% of non-ionic surfactant, 20%-30% of water-soluble organic solvent and water; the sum of the mass fractions of each component is 100%;

[0019] The hydroxylamine compound is N-methylhydroxylamine and / or N,N-diethylhydroxylamine;

[0020] The resist is catechol;

[0021] The chelating agent is ethylenediaminetetraacetic acid;

[0022] The non-ionic surfactant is EO-PO polymer L42;

[0023] The water-soluble organic solvent is dimethyl sulfoxide;

[0024] The water is deionized water.

[0025] In some embodiments, the hydroxylamine compound cleaning solution consists of the following components in mass fractions: the above-mentioned hydroxylamine compounds (including the types and mass fractions of hydroxylamine compounds), the above-mentioned resist (including the types and mass fractions of resist), the above-mentioned chelating agent (including the types and mass fractions of chelating agent), 0.01-5% of non-ionic surfactant (including the types and mass fractions of non-ionic surfactant), 0.01-5% of water-soluble organic solvent (including the types and mass fractions of water-soluble organic solvent) and 0.01-5% of water (including the types and mass fractions of water); the sum of the mass fractions of each component is 100%.

[0026] In some embodiments, the hydroxylamine compound cleaning solution consists of the following components:

[0027] (1): 5% of N-methylhydroxylamine, 2% of catechol, 0.5% of ethylenediaminetetraacetic acid, 1% of EO-PO polymer L42, 25% of dimethyl sulfoxide and the balance of deionized water;

[0028] (2): 10% N-methylhydroxylamine, 2% catechol, 0.5% ethylenediaminetetraacetic acid, 1% EO-PO polymer L42, 25% dimethyl sulfoxide, and the balance deionized water;

[0029] (3): 15% N-methylhydroxylamine, 2% catechol, 0.5% ethylenediaminetetraacetic acid, 1% EO-PO polymer L42, 25% dimethyl sulfoxide, and the balance deionized water;

[0030] (4): 20% N-methylhydroxylamine, 2% catechol, 0.5% ethylenediaminetetraacetic acid, 1% EO-PO polymer L42, 25% dimethyl sulfoxide, and the balance deionized water;

[0031] (5): 5% N,N-diethylhydroxylamine, 2% catechol, 0.5% ethylenediaminetetraacetic acid, 1% EO-PO polymer L42, 25% dimethyl sulfoxide, and the balance deionized water;

[0032] (6): 10% N,N-diethylhydroxylamine, 2% catechol, 0.5% ethylenediaminetetraacetic acid, 1% EO-PO polymer L42, 25% dimethyl sulfoxide, and the balance deionized water;

[0033] (7): 15% N,N-diethylhydroxylamine, 2% catechol, 0.5% ethylenediaminetetraacetic acid, 1% EO-PO polymer L42, 25% dimethyl sulfoxide, and the balance deionized water;

[0034] (8): 20% N,N-diethylhydroxylamine, 2% catechol, 0.5% ethylenediaminetetraacetic acid, 1% EO-PO polymer L42, 25% dimethyl sulfoxide, and the balance deionized water.

[0035] In some embodiments, in the preparation method, the mixing is preferably adding the solid in the raw materials to the liquid and stirring evenly.

[0036] In some embodiments, in the preparation method, the mixing temperature is preferably room temperature.

[0037] In some embodiments, in the preparation method, the stirring time is 12 - 48 hours, preferably 20 hours; the stirring temperature does not exceed 60°C, preferably 50°C.

[0038] The present invention also provides a hydroxylamine compound cleaning solution, and the components of the hydroxylamine compound cleaning solution are as described above.

[0039] The present invention also provides an application of the hydroxylamine compound cleaning solution in cleaning wafers after plasma etching and ashing.

[0040] In the present invention, the room temperature refers to 10 - 30 °C.

[0041] On the basis of conforming to the common knowledge in the art, the above preferred conditions can be combined arbitrarily to obtain various preferred examples of the present invention.

[0042] The reagents and raw materials used in the present invention are all commercially available.

[0043] The positive and progressive effects of the present invention are as follows: The cleaning agent is safe and environmentally friendly, solves the problem of high cost caused by the fixed source of raw materials, reduces the cost, and is safe and reliable. Detailed implementation manners

[0044] The present invention will be further illustrated below by way of examples, but the present invention is not limited to the scope of the described examples. For the experimental methods without specific conditions noted in the following examples, they are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0045] Preparation of the cleaning solution:

[0046] Mix the raw material components of the cleaning solution according to the types and contents in the following table to prepare the cleaning solution.

[0047] The preparation method is carried out as follows: Mix all the raw material components evenly. Among them, the mixing method is to add the solid components to the liquid components, stir for 20 hours, the stirring temperature is 50 °C, and stir evenly.

[0048] In the following examples, where the specific operating temperature is not limited, it means that the operation is carried out under room temperature conditions.

[0049] In the present invention, the room temperature refers to 10 - 30 °C.

[0050] Table 1 Types of raw material components of the cleaning solution

[0051]

[0052]

[0053] Table 2 Dosage of raw material components of the cleaning solution

[0054]

[0055]

[0056] Table 3 Mass fractions of raw material components of the cleaning solution

[0057]

[0058] In the table, "the balance" means, in each example, 100% minus the mass percentage of other components.

[0059] Testing method:

[0060] Test the etching rates of aluminum and non-metal (plasma enhanced TEOS (PETEOS)) silicon wafers and clean the wafers after plasma etching and ashing for three different types.

[0061] I. Testing method for the metal corrosion rate of the cleaning solution:

[0062] 1. Use a Napson four-point probe to measure the initial resistance value (Rs1) of a 4×4 cm aluminum blank silicon wafer.

[0063] 2. Immerse the 4×4 cm aluminum blank silicon wafer in a solution that has been pre-heated to a set temperature of 70 °C for 60 minutes.

[0064] 3. Take out the 4×4 cm aluminum blank silicon wafer, rinse it, dry it with high-purity nitrogen, and then use a Napson four-point probe to measure the resistance value (Rs2) of the 4×4 cm aluminum blank silicon wafer.

[0065] 4. Input the above resistance value and immersion time into a suitable program to calculate its corrosion rate.

[0066] II. Testing method for the non-metal corrosion rate of the cleaning solution:

[0067] 1. Use a Nanospec 6100 thickness gauge to measure the thickness (T1) of a 4×4 cm PETEOS silicon wafer.

[0068] 2. Immerse the 4×4 cm PETEOS silicon wafer in a solution that has been pre-heated to a set temperature of 70 °C for 60 minutes.

[0069] 3. Take out the 4×4 cm PETEOS silicon wafer, rinse it, dry it with high-purity nitrogen, and then use a Nanospec 6100 thickness gauge to measure the thickness (T2) of the 4×4 cm PETEOS silicon wafer.

[0070] 4. Input the above thickness value and immersion time into a suitable program to calculate its corrosion rate.

[0071] III. Method for wafer cleaning

[0072] 1. Place the wafer to be cleaned into a solution that has been pre-heated to a set temperature.

[0073] 2. Immerse the wafer according to the principle that the metal wires are immersed for 20 minutes and the channels and metal pads are immersed for 30 minutes.

[0074] 3. After the immersion time, take out the wafer, rinse it, dry it with high-purity nitrogen, and send it for SEM testing.

[0075] In each of the effect examples, when the metal corrosion rate is below 2 A / min, it is considered basically non-corrosive; when it is between 2 - 4 A / min, it is slightly corrosive; when it is between 4 - 15 A / min, it is moderately corrosive; and when it is above 15 A / min, it is severely corrosive.

[0076] In each of the effect examples, when the non-metal corrosion rate is below 0.5 A / min, it is considered basically non-corrosive; when it is between 0.5 - 4 A / min, it is slightly corrosive; when it is between 4 - 10 A / min, it is moderately corrosive; and when it is above 10 A / min, it is severely corrosive.

[0077] Table 4 Effect Examples

[0078]

[0079]

[0080] It can be seen from the experimental results that the hydroxylamine compound cleaning solution of the present invention has good cleaning effects and is superior to the hydroxylamine-containing cleaning solution in terms of corrosion of metals and non-metals.

Claims

1. A preparation method of a hydroxylamine compound cleaning solution, characterized in that, It includes the following steps: Mix the components of the hydroxylamine compound cleaning solution; the hydroxylamine compound cleaning solution includes components with the following mass fractions: 1-30% of hydroxylamine compounds, 1-5% of resist, 0.1-5% of chelating agent, 0.01-5% of non-ionic surfactant, 1-50% of water-soluble organic solvent and water; the sum of the mass fractions of each component is 100%.

2. The preparation method of the hydroxylamine compound cleaning solution according to claim 1, characterized in that, It satisfies one or more of the following conditions; (1) The hydroxylamine compound is selected from one or more of N-methylhydroxylamine, N-ethylhydroxylamine and N,N-diethylhydroxylamine; preferably N-methylhydroxylamine and / or N,N-diethylhydroxylamine; (2) The resist is selected from one or more of catechol, pyrogallol, alkyl gallate and alkyl catechol; preferably catechol; (3) The chelating agent is an organic acid, preferably selected from one or more of amino acids, ethylenediaminetetraacetic acid, lactic acid, benzoic acid, glycolic acid, malonic acid, maleic acid, salicylic acid, glyceric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid, malic acid, methanesulfonic acid, ethanesulfonic acid, hydroxyethylsulfonic acid, tartaric acid, citric acid, citrulline, gallic acid and gallic acid; preferably ethylenediaminetetraacetic acid; (4) The non-ionic surfactant is an EO-PO polymer, preferably selected from one or more of EO-PO polymer L42, EO-PO polymer L43 and EO-PO polymer L44; preferably EO-PO polymer L42; (5) The water-soluble organic solvent is a sulfone solvent and / or an alcohol solvent; preferably dimethyl sulfoxide and / or triethylene glycol; (6) The water is selected from one or more of deionized water, distilled water and ultrapure water; for example, deionized water.

3. The preparation method of the hydroxylamine compound cleaning solution according to claim 1, wherein, It satisfies one or more of the following conditions; (1) The mass fraction of the hydroxylamine compound is 1-30%; (2) The mass fraction of the resist is 1-5%; (3) The mass fraction of the chelating agent is 0.1-5%; (4) The mass fraction of the non-ionic surfactant is 0.01-5%; (5) The mass fraction of the water-soluble organic solvent is 1-50%.

4. The preparation method of the hydroxylamine compound cleaning solution according to claim 3, wherein, It satisfies one or more of the following conditions; (1) The mass fraction of the hydroxylamine compound is 2% to 25%; (2) The mass fraction of the resist is 1% to 4%; (3) The mass fraction of the chelating agent is 0.1% to 1%; (4) The mass fraction of the non-ionic surfactant is 0.5% to 4%; (5) The mass fraction of the water-soluble organic solvent is 10% to 40%.

5. The preparation method of the hydroxylamine compound cleaning solution according to claim 4, wherein, It satisfies one or more of the following conditions; (1) The mass fraction of the hydroxylamine compound is 5%, 10%, 15% or 20%; (2) The mass fraction of the resist is 2%; (3) The mass fraction of the chelating agent is 0.5%; (4) The mass fraction of the non-ionic surfactant is 1%; (5) The mass fraction of the water-soluble organic solvent is 25%.

6. The preparation method of the hydroxylamine compound cleaning solution according to claim 1, characterized in that, The hydroxylamine compound cleaning solution contains the following components by mass fraction: 5%-20% of hydroxylamine compound, 1.5%-2.5% of resist, 0.2%-0.8% of chelating agent, 0.5%-1.5% of non-ionic surfactant, 20%-30% of water-soluble organic solvent and water; the sum of the mass fractions of each component is 100%; The hydroxylamine compound is N-methylhydroxylamine and / or N,N-diethylhydroxylamine; The resist is catechol; The chelating agent is ethylenediaminetetraacetic acid; The non-ionic surfactant is EO-PO polymer L42; The water-soluble organic solvent is dimethyl sulfoxide; The water is deionized water.

7. The preparation method of the hydroxylamine compound cleaning solution according to claims 1-6, characterized in that, The hydroxylamine compound cleaning solution consists of the following components by mass fraction: the hydroxylamine compound as described in any one of claims 1-6, the resist as described in any one of claims 1-6, the chelating agent as described in any one of claims 1-6, the non-ionic surfactant as described in any one of claims 1-6, the water-soluble organic solvent as described in any one of claims 1-6 and the water as described in any one of claims 1-6; the sum of the mass fractions of each component is 100%.

8. The preparation method of the hydroxylamine compound cleaning solution according to claim 1, characterized in that, The hydroxylamine compound cleaning solution consists of the following components: (1): 5% of N-methylhydroxylamine, 2% of catechol, 0.5% of ethylenediaminetetraacetic acid, 1% of EO-PO polymer L42, 25% of dimethyl sulfoxide and the balance of deionized water; (2): 10% of N-methylhydroxylamine, 2% of catechol, 0.5% of ethylenediaminetetraacetic acid, 1% of EO-PO polymer L42, 25% of dimethyl sulfoxide and the balance of deionized water; (3): 15% of N-methylhydroxylamine, 2% of catechol, 0.5% of ethylenediaminetetraacetic acid, 1% of EO-PO polymer L42, 25% of dimethyl sulfoxide and the balance of deionized water; (4): 20% of N-methylhydroxylamine, 2% of catechol, 0.5% of ethylenediaminetetraacetic acid, 1% of EO-PO polymer L42, 25% of dimethyl sulfoxide and the balance of deionized water; (5): 5% of N,N-diethylhydroxylamine, 2% of catechol, 0.5% of ethylenediaminetetraacetic acid, 1% of EO-PO polymer L42, 25% of dimethyl sulfoxide and the balance of deionized water; (6): 10% of N,N-diethylhydroxylamine, 2% of catechol, 0.5% of ethylenediaminetetraacetic acid, 1% of EO-PO polymer L42, 25% of dimethyl sulfoxide and the balance of deionized water; (7): 15% of N,N-diethylhydroxylamine, 2% of catechol, 0.5% of ethylenediaminetetraacetic acid, 1% of EO-PO polymer L42, 25% of dimethyl sulfoxide and the balance of deionized water; (8): 20% of N,N-diethylhydroxylamine, 2% of catechol, 0.5% of ethylenediaminetetraacetic acid, 1% of EO-PO polymer L42, 25% of dimethyl sulfoxide and the balance of deionized water.

9. The preparation method of the hydroxylamine compound cleaning solution according to any one of claims 1-8, characterized in that, The mixing is to add the solid components to the liquid components and stir evenly.

10. The preparation method of the hydroxylamine compound cleaning solution according to claim 9, characterized in that, It satisfies one or more of the following conditions; (1) The temperature of the mixture is room temperature; (2) The stirring time is 12 - 48 hours, preferably 20 hours; (3) The temperature of the stirring does not exceed 60 °C, preferably 50 °C.

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