Cleaning solution for cleaning chip and preparation process of cleaning solution

Abstract

The invention relates to the technical field of chip cleaning solutions, in particular to a cleaning solution for cleaning a chip and a preparation process of the cleaning solution, and the cleaning solution comprises the following components in parts by weight: a main solvent, a composite functional additive, a multifunctional nano additive, an aldehyde group-containing compound and an amino group-containing compound, the main solvent comprises ultrapure water, a fluoro ester solvent and a temperature response type phase change solvent, the temperature response type phase change solvent is a fluoro tert-butyl alcohol derivative, the composite functional additive comprises a chelating agent, a surfactant and a corrosion inhibitor, and the multifunctional nano additive is a multi-core silicon dioxide nano capsule. According to the cleaning solution for cleaning the chip and the preparation process of the cleaning solution, the prepared cleaning solution has an excellent cleaning effect, can effectively remove various pollutants on the surface of the chip, has a good corrosion inhibition effect on the surface of the chip, and is good in stability and convenient to store and use.

Description

Technical Field

[0001] This invention relates to the field of chip cleaning solution technology, and in particular to a cleaning solution for cleaning chips and its preparation process. Background Technology

[0002] During chip manufacturing, various contaminants, such as metal ions, particulate impurities, and organic residues, can easily remain on the chip surface. These contaminants can severely affect chip performance and yield. Therefore, effective chip cleaning is a crucial step in the chip manufacturing process.

[0003] Currently, commonly used chip cleaning solutions have some shortcomings. Some cleaning solutions are ineffective and fail to completely remove various contaminants from the chip surface; some cleaning solutions can corrode the chip surface during the cleaning process, affecting chip quality; and some cleaning solutions have poor stability, and are prone to stratification and precipitation during storage and use, reducing the service life and effectiveness of the cleaning solution. Summary of the Invention

[0004] The purpose of this invention is to provide a cleaning solution for cleaning chips and its preparation process. The cleaning solution has excellent cleaning effect, can effectively remove various contaminants on the chip surface, has good corrosion inhibition effect on the chip surface, and has good stability, and is convenient to store and use.

[0005] To achieve the above objectives, the present invention provides a cleaning solution for cleaning chips, comprising, by weight, 60-80 parts of a main solvent, 15-30 parts of a composite functional additive, 5-10 parts of a multifunctional nano-additive, and 4-12 parts of an aldehyde-containing compound and an amino-containing compound. The main solvent includes ultrapure water, fluorinated ester solvents, and temperature-responsive phase change solvents. The temperature-responsive phase change solvent is a fluorinated tert-butanol derivative. The composite functional additives include chelating agents, surfactants, and corrosion inhibitors. The multifunctional nano-additive is a multi-core silica nanocapsule.

[0006] Preferably, the volume ratio of ultrapure water, fluorinated ester solvent, and temperature-responsive phase change solvent is 70:20:5-8.

[0007] Preferably, the fluoroester solvent includes one of methyl perfluorooctanoate, ethyl perfluorononanoate, and isopropyl perfluorodecanoate.

[0008] Preferably, the fluorotert-butanol derivative includes one of 1,1,1,3,3-pentafluoro-2-propanol, 2,2,3,3-tetrafluoro-1-propanol, and heptafluoro-2-butanol.

[0009] Preferably, the mass ratio of chelating agent, surfactant and corrosion inhibitor in the composite functional additive is 3-5:2-4:1-3.

[0010] Preferably, the chelating agent is a mixture of tetrasodium glutamate diacetate and aspartic acid diacetate in a mass ratio of 3:1.

[0011] Preferably, the surfactant includes one of 2,4,7,9-tetramethyl-5-decyn-4,7-diol, N-lauroyl-N-methylglucamide, and disodium lauryl ether sulfosuccinate.

[0012] Preferably, the corrosion inhibitor includes one or more of carboxybenzotriazole and 2-mercaptobenzimidazole.

[0013] Preferably, the particle size of the multi-core silica nanocapsules is 15-20 nm.

[0014] Preferably, the molar ratio of the aldehyde-containing compound to the amino-containing compound is 1:1; the aldehyde-containing compound includes one of formaldehyde, glutaraldehyde, and glyoxal; the amino-containing compound includes one of ethylenediamine, hexamethylenediamine, and aniline.

[0015] The present invention also provides a preparation process for the cleaning solution for cleaning chips as described above, comprising the following steps:

[0016] S1. Mix ultrapure water, fluorinated ester solvent and temperature-responsive phase change solvent to obtain the main solvent;

[0017] S2. Add part of the chelating agent, surfactant and corrosion inhibitor to the main solvent of S1, stir evenly, transfer to a continuous flow microchannel reactor, control the temperature at 30±0.5℃, the flow rate at 5mL / min, and use microwave-assisted activation with a power of 100W and a frequency of 40kHz. React for 10min to obtain mixture A.

[0018] S3. Using the deposition method, silica nanocarriers, the remaining corrosion inhibitors and the remaining chelating agents are placed in a supercritical reactor, CO2 is introduced until the pressure reaches 10 MPa, the temperature is raised to 40°C, and it is maintained for 1-1.5 hours to complete the loading process and prepare multi-core silica nanocapsules.

[0019] S4. Add the multi-core silica nanocapsules prepared in S3 to the mixture A in S2, and continue to react in a continuous flow microchannel reactor for 5 min to obtain mixture B.

[0020] S5. Mix the aldehyde-containing compound and the amino-containing compound, react at pH 5-6 and temperature 30-40℃ for 30 min, then add to the mixture B in S4, mix evenly, and filter through a ceramic membrane to obtain the cleaning solution.

[0021] Preferably, the total amount of aldehyde-containing compounds and amino-containing compounds accounts for 5%-10% of the total mass of mixture B.

[0022] Therefore, the present invention employs the above-mentioned cleaning solution for cleaning chips and its preparation process, which has the following beneficial effects:

[0023] (1) The main solvent in this invention is a mixture of ultrapure water, fluorinated ester solvent and fluorinated tert-butanol derivative. Fluorinated ester solvent and fluorinated tert-butanol derivative have good solubility and permeability, and can effectively dissolve organic pollutants and particulate impurities on the chip surface. The temperature-responsive phase change solvent fluorinated tert-butanol derivative will undergo phase change at different temperatures, and its state can be adjusted according to cleaning requirements to improve the cleaning effect.

[0024] (2) The chelating agent in the composite functional additive of the present invention can chelate with the metal ions on the chip surface to effectively remove metal impurities on the chip surface; the surfactant can reduce the surface tension of the cleaning solution, improve the wettability of the cleaning solution on the chip surface, and enhance the cleaning effect; the corrosion inhibitor can form a protective film on the chip surface to prevent the chip from being corroded.

[0025] (3) The multifunctional nano-auxiliary multi-core silica nanocapsules in this invention have a large specific surface area and porosity, which can adsorb contaminants on the chip surface. At the same time, its multi-core structure can slowly release the corrosion inhibitor and chelating agent loaded on it, thus extending the service life of the cleaning solution.

[0026] (4) In this invention, the condensation reaction between the aldehyde-containing compound and the amino-containing compound forms a dynamic covalent cross-linked network with a Schiff base structure, which can further enhance the stability and cleaning effect of the cleaning solution. Furthermore, impurities can be removed by filtration through a ceramic membrane, thereby improving the purity of the cleaning solution.

[0027] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0028] Figure 1 This is a schematic diagram of the chip after cleaning with the cleaning solutions of Example 2 and Comparative Example 1 of the present invention. Figure 1 In the diagram, A is a schematic diagram of the chip after cleaning with the cleaning solution of Embodiment 2 of the present invention. Figure 1 B in the diagram is a schematic diagram of the chip after cleaning with the cleaning solution of Comparative Example 1 of this invention. Detailed Implementation

[0029] The present invention will be further described below with reference to the accompanying drawings and embodiments. Unless otherwise defined, the technical or scientific terms used in this invention should be understood in their ordinary sense by those skilled in the art. The features mentioned above or in the specific examples mentioned in this invention can be combined arbitrarily, and these specific embodiments are only used to illustrate the invention and are not intended to limit the scope of the invention.

[0030] Example 1

[0031] This invention provides a cleaning solution for cleaning chips, comprising, by weight, 60 parts of a main solvent, 15 parts of a composite functional additive, 5 parts of a multifunctional nano-additive, and 4 parts of an aldehyde-containing compound and an amino-containing compound.

[0032] In the main solvent, the volume ratio of ultrapure water, ethyl perfluorononanoate, and 2,2,3,3-tetrafluoro-1-propanol is 70:20:5.

[0033] In the composite functional additive, the mass ratio of chelating agent, surfactant, and corrosion inhibitor is 3:2:1. The chelating agent is a mixture of tetrasodium glutamate diacetate and aspartic acid diacetate in a mass ratio of 3:1; the surfactant is N-lauroyl-N-methylglucamide; and the corrosion inhibitor is 2-mercaptobenzimidazole.

[0034] The multifunctional nano-additive is a multi-core silica nanocapsule with a particle size of 15 nm.

[0035] The compound containing an aldehyde group is formaldehyde, and the compound containing an amino group is hexamethylenediamine, with a molar ratio of 1:1.

[0036] The preparation process of the cleaning solution for cleaning chips described above includes the following steps:

[0037] S1. Mix ultrapure water, ethyl perfluorononanoate, and 2,2,3,3-tetrafluoro-1-propanol in the volume ratio described above to obtain the main solvent.

[0038] S2. Add two-thirds of the chelating agent, all of the surfactant, and one-third of the corrosion inhibitor to the main solvent in S1. After stirring evenly, transfer to a continuous flow microchannel reactor, control the temperature at 30±0.5℃, the flow rate at 5mL / min, and simultaneously use microwave-assisted activation with a power of 100W and a frequency of 40kHz. React for 10min to obtain mixture A.

[0039] S3. Using the deposition method, silica nanocarriers, the remaining corrosion inhibitors and the remaining chelating agents are placed in a supercritical reactor, CO2 is introduced until the pressure reaches 10 MPa, the temperature is raised to 40°C, and it is maintained for 1 hour to complete the loading process and prepare multi-core silica nanocapsules.

[0040] S4. Add the multi-core silica nanocapsules prepared in S3 to the mixture A in S2, and continue to react in a continuous flow microchannel reactor for 5 min to obtain mixture B.

[0041] S5. Mix formaldehyde and hexamethylenediamine and react at pH 5 and 30℃ for 30 min. Then add it to mixture B from S4 (the total amount of which accounts for 5% of the total mass of mixture B). After mixing evenly, filter through a 0.01μm ceramic membrane to obtain the cleaning solution.

[0042] Example 2

[0043] This invention provides a cleaning solution for cleaning chips, comprising, by weight, 70 parts of a main solvent, 22 parts of a composite functional additive, 8 parts of a multifunctional nano-additive, and 10 parts of an aldehyde-containing compound and an amino-containing compound.

[0044] In the main solvent, the volume ratio of ultrapure water, methyl perfluorooctanoate, and 1,1,1,3,3-pentafluoro-2-propanol is 70:20:6.

[0045] In the composite functional additive, the mass ratio of chelating agent, surfactant, and corrosion inhibitor is 4:3:2. The chelating agent is a mixture of tetrasodium glutamate diacetate and aspartic acid diacetate in a mass ratio of 3:1; the surfactant is 2,4,7,9-tetramethyl-5-decyn-4,7-diol; and the corrosion inhibitor is carboxybenzotriazole.

[0046] The multifunctional nano-additive is a multi-core layered silica nanocapsule with a particle size of 17 nm.

[0047] The compound containing an aldehyde group is glutaraldehyde, and the compound containing an amino group is ethylenediamine, with a molar ratio of 1:1.

[0048] The preparation process of the cleaning solution for cleaning chips described above includes the following steps:

[0049] S1. Mix ultrapure water, methyl perfluorooctanoate and 1,1,1,3,3-pentafluoro-2-propanol in the volume ratio described above to obtain the main solvent.

[0050] S2. Add half of the chelating agent, all of the surfactant and half of the corrosion inhibitor to the main solvent in S1. After stirring evenly, transfer to a continuous flow microchannel reactor, control the temperature at 30±0.5℃, the flow rate at 5mL / min, and simultaneously use microwave-assisted activation with a power of 100W and a frequency of 40kHz. React for 10min to obtain mixture A.

[0051] S3. Using a deposition method, silica nanocarriers, the remaining corrosion inhibitors and the remaining chelating agents are placed in a supercritical reactor, CO2 is introduced until the pressure reaches 10 MPa, the temperature is raised to 40°C, and maintained for 1.2 hours to complete the loading process and prepare multi-core silica nanocapsules.

[0052] S4. Add the multi-core silica nanocapsules prepared in S3 to the mixture A in S2, and continue to react in a continuous flow microchannel reactor for 5 min to obtain mixture B.

[0053] S5. Mix glutaraldehyde and ethylenediamine and react at pH 5.5 and 35℃ for 30 min. Then add the mixture to mixture B in S4 (the total amount of which accounts for 10% of the total mass of mixture B). After mixing evenly, filter through a 0.01μm ceramic membrane to obtain the cleaning solution.

[0054] Example 3

[0055] This invention provides a cleaning solution for cleaning chips, comprising, by weight, 80 parts of main solvent, 30 parts of composite functional additive, 10 parts of multifunctional nano-additive, and 12 parts of aldehyde-containing compound and amino-containing compound.

[0056] In the main solvent, the volume ratio of ultrapure water, isopropyl perfluorodecanoate, and heptafluoro-2-butanol is 70:20:8.

[0057] In the composite functional additive, the mass ratio of chelating agent, surfactant, and corrosion inhibitor is 5:4:3. The chelating agent is a mixture of tetrasodium glutamate diacetate and aspartic acid diacetate in a mass ratio of 3:1; the surfactant is disodium lauryl ether sulfosuccinate; and the corrosion inhibitor is a mixture of carboxybenzotriazole and 2-mercaptobenzimidazole in a mass ratio of 1:1.

[0058] The multifunctional nano-additive is a multi-core layered silica nanocapsule with a particle size of 20 nm.

[0059] The compound containing an aldehyde group is glyoxal, and the compound containing an amino group is aniline, with a molar ratio of 1:1.

[0060] The preparation process of the cleaning solution for cleaning chips described above includes the following steps:

[0061] S1. Mix ultrapure water, isopropyl perfluorodecanoate, and heptafluoro-2-butanol in the volume ratio described above to obtain the main solvent.

[0062] S2. Add three-quarters of the chelating agent, all of the surfactant, and half of the corrosion inhibitor to the main solvent in S1. After stirring evenly, transfer to a continuous flow microchannel reactor, control the temperature at 30±0.5℃, the flow rate at 5mL / min, and simultaneously use microwave-assisted activation with a power of 100W and a frequency of 40kHz. React for 10min to obtain mixture A.

[0063] S3. Using a deposition method, silica nanocarriers, the remaining corrosion inhibitors and the remaining chelating agents are placed in a supercritical reactor, CO2 is introduced until the pressure reaches 10 MPa, the temperature is raised to 40°C, and maintained for 1.5 hours to complete the loading process and prepare multi-core silica nanocapsules.

[0064] S4. Add the multi-core silica nanocapsules prepared in S3 to the mixture A in S2, and continue to react in a continuous flow microchannel reactor for 5 min to obtain mixture B.

[0065] S5. Mix glyoxal and aniline, react at pH 6 and temperature 40℃ for 30 min, then add to mixture B of S4 (the total amount of which accounts for 10% of the total mass of mixture B). After mixing evenly, filter through a ceramic membrane to obtain the cleaning solution.

[0066] Comparative Example 1

[0067] Compared to Example 2, the main solvent does not contain a temperature-responsive phase change solvent, but all other aspects are the same as in Example 2.

[0068] Comparative Example 2

[0069] Compared to Example 2, the composite functional additive does not contain a chelating agent, but all other aspects are the same as in Example 2.

[0070] Comparative Example 3

[0071] Compared to Example 2, this one does not contain the multifunctional nano-additive; all other aspects are the same as in Example 2.

[0072] Comparative Example 4

[0073] Compared with Example 2, no aldehyde-containing compounds or amino-containing compounds were added, and all other aspects were the same as in Example 2.

[0074] Chips from the same batch with consistent surface contamination were selected and cleaned using the cleaning solutions from Examples 1-3 and Comparative Examples 1-4, respectively, under identical cleaning conditions (temperature 35℃, time 5 min). After cleaning, the residual metal ions, the number of particulate impurities, and the corrosion status of the chip surface were measured. The stability of the cleaning solution was also tested (whether it separated after 30 days). The results are shown in Table 1.

[0075] Table 1. Chips after cleaning with different cleaning solutions

[0076]

[0077]

[0078] Figure 1 This is a schematic diagram of a chip after cleaning with the cleaning solutions of Embodiment 2 and Comparative Example 1 of the present invention, in conjunction with... Figure 1 As shown in Table 1, the cleaning solutions of Examples 1-3 of this invention are superior to those of Comparative Examples 1-4 in terms of residual metal ions, number of particulate impurities, corrosion resistance, and stability. Specifically, Comparative Example 1, lacking a temperature-responsive phase change solvent, exhibited reduced cleaning effectiveness and stability; Comparative Example 2, lacking a chelating agent, showed a significant increase in residual metal ions; Comparative Example 3, lacking multifunctional nano-auxiliaries, suffered reduced particulate impurity removal and corrosion resistance; and Comparative Example 4, without the addition of aldehyde-containing and amino-containing compounds, showed decreased cleaning effectiveness and significantly worsened stability, exhibiting obvious stratification. This fully demonstrates that the components and preparation process of the cleaning solution of this invention work synergistically to achieve excellent cleaning results and good stability.

[0079] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A cleaning solution for cleaning chips, characterized in that: The product comprises, by weight, 60-80 parts of main solvent, 15-30 parts of composite functional additives, 5-10 parts of multifunctional nano-additives, and 4-12 parts of aldehyde-containing compounds and amino-containing compounds. The main solvents include ultrapure water, fluorinated ester solvents, and temperature-responsive phase change solvents. The temperature-responsive phase change solvent is a fluorinated tert-butanol derivative. The composite functional additives include chelating agents, surfactants, and corrosion inhibitors. The multifunctional nano-additives are multi-core silica nanocapsules.

2. The cleaning solution for cleaning chips according to claim 1, characterized in that: The volume ratio of ultrapure water, fluorinated ester solvents, and temperature-responsive phase change solvents is 70:20:5-8.

3. The cleaning solution for cleaning chips according to claim 1, characterized in that: Fluorinated ester solvents include one of the following: methyl perfluorooctanoate, ethyl perfluorononanoate, and isopropyl perfluorodecanoate.

4. The cleaning solution for cleaning chips according to claim 1, characterized in that: Fluorinated tert-butanol derivatives include one of 1,1,1,3,3-pentafluoro-2-propanol, 2,2,3,3-tetrafluoro-1-propanol, and heptafluoro-2-butanol.

5. The cleaning solution for cleaning chips according to claim 1, characterized in that: The mass ratio of chelating agent, surfactant and corrosion inhibitor in composite functional additives is 3-5:2-4:1-3.

6. The cleaning solution for cleaning chips according to claim 1, characterized in that: The chelating agent is a mixture of tetrasodium glutamate diacetate and aspartic acid diacetate in a mass ratio of 3:

1.

7. The cleaning solution for cleaning chips according to claim 1, characterized in that: Surfactants include one of 2,4,7,9-tetramethyl-5-decyn-4,7-diol, N-lauroyl-N-methylglucamide, and disodium lauryl ether sulfosuccinate.

8. The cleaning solution for cleaning chips according to claim 1, characterized in that: Corrosion inhibitors include one or more of carboxybenzotriazole and 2-mercaptobenzimidazole.

9. The cleaning solution for cleaning chips according to claim 1, characterized in that: The molar ratio of aldehyde-containing compounds to amino-containing compounds is 1:1; aldehyde-containing compounds include one of formaldehyde, glutaraldehyde, and glyoxal; amino-containing compounds include one of ethylenediamine, hexamethylenediamine, and aniline.

10. A process for preparing a cleaning solution for cleaning chips as described in any one of claims 1-9, characterized in that: Includes the following steps: S1. Mix ultrapure water, fluorinated ester solvent and temperature-responsive phase change solvent to obtain the main solvent; S2. Add part of the chelating agent, surfactant and corrosion inhibitor to the main solvent of S1, stir evenly, transfer to a continuous flow microchannel reactor, control the temperature at 30±0.5℃, the flow rate at 5mL / min, and use microwave-assisted activation with a power of 100W and a frequency of 40kHz. React for 10min to obtain mixture A. S3. Using the deposition method, silica nanocarriers, the remaining corrosion inhibitors and the remaining chelating agents are placed in a supercritical reactor, CO2 is introduced until the pressure reaches 10 MPa, the temperature is raised to 40°C, and it is maintained for 1-1.5 hours to complete the loading process and prepare multi-core silica nanocapsules. S4. Add the multi-core silica nanocapsules prepared in S3 to the mixture A in S2, and continue to react in a continuous flow microchannel reactor for 5 min to obtain mixture B. S5. Mix the aldehyde-containing compound and the amino-containing compound, react at pH 5-6 and temperature 30-40℃ for 30 min, then add to the mixture B in S4, mix evenly, and filter through a ceramic membrane to obtain the cleaning solution.

Images