Electronic grade tetramethylammonium hydroxide organic solution, its production process and application

Abstract

The application discloses electronic-grade tetramethylammonium hydroxide organic solution, a production process and application thereof, and belongs to the technical field of wet electronic chemicals. The application takes industrial-grade TMAH aqueous solution as raw material, and sequentially carries out ion exchange purification, bubbling evaporation and solvent replacement, concentration adjustment and multi-stage filtration treatment to obtain the electronic-grade tetramethylammonium hydroxide organic solution. ‑ The ion exchange purification adopts tetramethylammonium cation exchange resin pre and OH After the ion exchange treatment, the solution is further treated by using the vacuum evaporation technology of inert gas bubbling, the TMAH aqueous solution and propylene glycol are synchronously put into an evaporation tower, dehydration and solvent replacement are synchronously completed in the bubbling evaporation tower, high-purity nitrogen gas is used for bubbling to improve the dehydration efficiency, and the product purity is improved.

Description

Technical Field

[0001] This invention belongs to the field of wet electronic chemicals technology, specifically relating to an electronic-grade tetramethylammonium hydroxide organic solution, its production process, and its application. Background Technology

[0002] Tetramethylammonium hydroxide (TMAH) is a strongly alkaline organic compound that is hygroscopic, soluble in water and various organic solvents, and widely used in high-end electronic fields such as semiconductor photolithography and development.

[0003] Commercially available TMAH products are mostly electrolytically produced TMAH aqueous solutions, which have high water and metal impurity content. Downstream wet electronic chemicals (such as stripping solutions, etching solutions, and cleaning solutions) require high-purity TMAH organic solutions. Currently, the common processing technology for electronic-grade TMAH organic solutions involves using electronic-grade TMAH aqueous solutions as raw materials, followed by distillation / evaporation dehydration, and then mixing and concentrating with electronic-grade organic solvents (such as IPA and PG). This process not only easily introduces impurities and makes concentration adjustment difficult, but TMAH is also prone to thermal decomposition during distillation / evaporation dehydration, resulting in a finished product that fails to meet the high purity requirements of electronic-grade solutions. Furthermore, the raw material requirements are high, making it impossible to directly use industrial-grade TMAH as a raw material. Therefore, developing a production process for directly producing electronic-grade TMAH organic solutions from industrial-grade TMAH has significant practical value. Summary of the Invention

[0004] This invention provides an electronic-grade tetramethylammonium hydroxide organic solution, its production process, and its application, which can solve the problems of high raw material requirements and high impurity content in the finished product of the production of electronic-grade tetramethylammonium hydroxide organic solution in the prior art.

[0005] The objective of this invention can be achieved through the following technical solutions: A process for producing an electronic-grade tetramethylammonium hydroxide organic solution includes the following steps: S1. Industrial-grade TMAH aqueous solution is passed through ion exchange columns connected in series with cation and anion columns to remove metal ions and anion impurities. S2. The TMAH aqueous solution after ion exchange treatment enters the bubble evaporator, propylene glycol is added simultaneously, high-purity nitrogen gas is bubbled into the liquid phase to generate microbubbles, negative pressure evaporation and dehydration are carried out to form TMAH organic solution intermediate. S3 and TMAH organic solution intermediates are introduced into the concentration tank, and the concentration is monitored online. Propylene glycol is added and mixed according to the TMAH concentration requirements to adjust the concentration. S4. The concentrated solution is filtered through a multi-stage filter cartridge to obtain an electronic grade tetramethylammonium hydroxide organic solution.

[0006] Furthermore, the cation exchange column is packed with a tetramethylammonium-type strongly acidic cation exchange resin.

[0007] Furthermore, the preparation steps of the tetramethylammonium type strongly acidic cation exchange resin are as follows: After packing the strongly acidic cation exchange resin column, slowly flow 4-5 wt% hydrochloric acid through the resin, using 3-4 times the resin volume at a flow rate of 1.5 times the bed volume per hour. After the hydrochloric acid is completely introduced, soak for 4-6 hours to remove the hydrochloric acid. Rinse the resin with ultrapure water until the effluent is neutral. After stopping the rinsing, slowly flow 4-5 wt% electronic-grade TMAH aqueous solution through the resin, using 3-4 times the resin volume at a flow rate of 1.5 times the bed volume per hour. After the electronic-grade TMAH aqueous solution is completely introduced, soak for 4-6 hours and rinse with ultrapure water until the effluent is neutral.

[0008] Furthermore, the anion exchange column is packed with OH... - A type of strongly basic anion exchange resin.

[0009] Furthermore, the OH - The preparation steps of the strong basic anion exchange resin are as follows: After packing the strongly basic anion exchange resin column, slowly flow 4-5 wt% hydrochloric acid through the resin, using 3-4 times the resin volume at a flow rate of 1.5 times the bed volume per hour. After the hydrochloric acid is completely introduced, soak for 4-6 hours to remove the hydrochloric acid. Rinse the resin with ultrapure water until the effluent is neutral. After stopping the rinsing, slowly flow 4-5 wt% sodium hydroxide solution through the resin, using 3-4 times the resin volume at a flow rate of 1.5 times the bed volume per hour. After the sodium hydroxide solution is completely introduced, soak for 4-6 hours and rinse with ultrapure water until the effluent is neutral.

[0010] Furthermore, the volume hourly space velocity (HSV) of the industrial-grade TMAH aqueous solution passing through the series ion exchange column is 0.8-2.0 h⁻¹. -1 The temperature of industrial-grade TMAH aqueous solution is 25-45℃.

[0011] Furthermore, the absolute pressure inside the bubbling evaporator is 40-100 kPa, and the solution temperature is 50-60℃.

[0012] Further, in step S2, the mass ratio of propylene glycol to tetramethylammonium hydroxide in the TMAH aqueous solution is 3:1-5:1.

[0013] Furthermore, the high-purity nitrogen gas has a temperature of 60-70℃, a purity of ≥99.999%, and a gas velocity of 0.5-1.0m / s.

[0014] Furthermore, the water content in the TMAH organic solution intermediate is <0.5wt%.

[0015] Furthermore, the mixing speed is 300-500 r / min, and the mixing time is 15-20 min.

[0016] Furthermore, the multi-stage filter cartridge uses a three-stage perfluorinated filter cartridge in series, with filtration accuracies of 1μm, 0.1μm and 0.05μm respectively, and an operating temperature of 20-30℃.

[0017] The present invention also provides an electronic grade tetramethylammonium hydroxide organic solution, which is produced by the production process described above. The concentration of the electronic grade tetramethylammonium hydroxide organic solution is 10-20 wt%, the total metal ion content is ≤30 ppb, the chloride ion content is ≤100 ppb, and the number of particles greater than or equal to 0.1 μm is ≤100 pcs / mL.

[0018] The present invention also provides an application of an electronic-grade tetramethylammonium hydroxide organic solution, which, as described above, can be used to prepare a photoresist cleaning agent.

[0019] The beneficial effects of this invention are: This invention uses industrial-grade TMAH aqueous solution as raw material, which undergoes sequential ion exchange purification, bubbling evaporation and solvent replacement, concentration adjustment, and multi-stage filtration to obtain electronic-grade tetramethylammonium hydroxide organic solution. By pre-converting the cation exchange resin to the tetramethylammonium form, the exchangeable ions on the resin are made completely consistent with the bulk cations in the solution, thus exchanging the Na+ in the raw material. + K + Fe 3+ Metal impurities, to remove metal impurities, OH - OH groups on type anion exchange resin - Exchange Cl - SO4 2- Anions, the OH- ions exchanged -Completely integrated into the solution, the transforming ion exchange resin removes impurity ions from the solution without introducing other impurity ions, significantly reducing the impurity ion content in the product. After ion exchange treatment, the solution is further processed using inert gas bubbling vacuum evaporation technology. TMAH aqueous solution and propylene glycol are simultaneously introduced into the evaporation tower. Propylene glycol has a much higher boiling point than water, so water is preferentially removed during evaporation. TMAH is gradually replaced by the propylene glycol medium, yielding a TMAH organic solution intermediate. Dehydration and solvent replacement are completed simultaneously in the bubbling evaporation tower. High-purity nitrogen bubbling increases the gas-liquid interface contact area, enhances water evaporation mass transfer, reduces water vapor partial pressure, and improves dehydration efficiency. Furthermore, nitrogen can carry away trace amounts of dissolved oxygen, reducing the dissolved oxygen content in the finished product. Highly efficient dehydration is achieved at temperatures far below the TMAH decomposition temperature, significantly reducing the risk of thermal decomposition of tetramethylammonium hydroxide and improving product purity. This invention overcomes the limitation of existing technologies that require electronic-grade TMAH aqueous solutions as a starting point. Through a combination of ion exchange, evaporation dehydration, and multi-stage filtration, the product meets the high purity requirements of downstream wet electronic chemicals. The production process is suitable for large-scale production, and the product concentration is stable and controllable. Detailed Implementation

[0020] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0021] Preparation Example 1 Preparation of tetramethylammonium type strong acid cation exchange resin: The washed strong acid cation exchange resin (Amberlyst® 15) was packed into a front column with an inner diameter of 5.5 cm, a height of 78 cm, and a diameter-to-height ratio of 1:14. 4 wt% hydrochloric acid was slowly flowed through the resin at a volume of 4 times the resin volume and a flow rate of 1.5 times the bed volume per hour. After the hydrochloric acid was completely introduced, the resin was soaked for 5 hours to remove the hydrochloric acid. The resin was then rinsed with ultrapure water until the effluent was neutral. After rinsing was stopped, 4 wt% electronic grade TMAH aqueous solution was slowly flowed through the resin at a volume of 4 times the resin volume and a flow rate of 1.5 times the bed volume per hour. After the electronic grade TMAH aqueous solution was completely introduced, the resin was soaked for 6 hours and then rinsed with ultrapure water until the effluent was neutral.

[0022] Preparation Example 2 Preparation of OH - Type of strongly basic anion exchange resin: The washed strong base anion exchange resin (type 201×7) was packed into a rear column with an inner diameter of 5.5 cm, a height of 78 cm, and a diameter-to-height ratio of 1:14. 4 wt% hydrochloric acid was slowly flowed through the resin at a volume of 4 times the resin volume and a flow rate of 1.5 times the bed volume per hour. After the hydrochloric acid was completely introduced, the column was soaked for 5 hours to remove the hydrochloric acid. The resin was then rinsed with ultrapure water until the effluent was neutral. After rinsing was stopped, 4 wt% sodium hydroxide solution was slowly flowed through the resin at a volume of 3 times the resin volume and a flow rate of 1.5 times the bed volume per hour. After the sodium hydroxide solution was completely introduced, the column was soaked for 5 hours and then rinsed with ultrapure water until the effluent was neutral.

[0023] Example 1 The front and rear columns obtained from Preparation Example 1 and Preparation Example 2 were connected in series and incubated with an industrial-grade TMAH aqueous solution (25 wt%, total metal ion content of 5.4 ppm, including potassium, calcium, sodium, magnesium, iron, and chloride ion content of 254.8 ppm) at 35°C for 1.5 h. -1 The volume hourly space velocity (VHSV) of the TMAH solution is sequentially passed through the front and rear columns of the ion exchange column to remove metal ions and anionic impurities. The TMAH aqueous solution exiting the ion exchange column enters the bubble evaporator, where propylene glycol is added simultaneously. The mass ratio of propylene glycol to tetramethylammonium hydroxide in the TMAH aqueous solution is 4:1. The tower is lined with polytetrafluoroethylene (PTFE), and a high-purity nitrogen microbubble distributor is built into the bottom of the tower. An absolute pressure sensor is installed inside the tower. Preheated high-purity nitrogen (temperature 60℃, purity ≥99.999%) is introduced into the high-purity nitrogen microbubble distributor at a gas velocity of 0.8 m / s. (The high-purity nitrogen microbubble distributor structure: uses PTFE microporous spiral coil, coil specification DN25, outer diameter 25mm, wall thickness 3mm, micropore diameter 1.0mm, and pore spacing 100mm.) The centerline diameter is 960mm, the coil spacing is 100mm, and there are 10 coils in total, with a total unfolded length of approximately 30m. All coils are immersed in the liquid phase at the bottom of the column (one end is closed, and the other end is connected to a high-purity nitrogen preheating pipeline), generating microbubbles of 0.1-0.5mm. The absolute pressure inside the column is controlled at 60kPa, the solution temperature at 55℃, and the material residence time at 45min. The solution in the bubbling evaporator undergoes dehydration and solvent replacement to obtain the TMAH organic solution intermediate. Referring to standard GB / T 606-2003, the water content of the TMAH organic solution intermediate is determined using the Karl Fischer volumetric method, and the water content is 0.42wt%. The TMAH organic solution intermediate is fed into a concentration tank equipped with an online concentration meter. Based on the monitored concentration, propylene glycol is added, and stirring is initiated at 400 rpm for 20 minutes. The solution concentration is then adjusted to 10 wt%. The concentrated solution is then filtered through a three-stage perfluorinated filter series filter. The filtration accuracies of the three perfluorinated filter series filters are 1 μm, 0.1 μm, and 0.05 μm, respectively. The operating temperature is 25°C, and the flow rate is 0.5 m³ / min. 3 / h, after filtration, an electronic-grade tetramethylammonium hydroxide organic solution was obtained. The total metal ion content was 26ppb, the chloride ion content was 54ppb, and the number of particles greater than or equal to 0.1um was ≤100pcs / mL.

[0024] Example 2 The only difference from Example 1 is that a 10wt% industrial-grade TMAH aqueous solution is used as the raw material.

[0025] The front and rear columns obtained from Preparation Example 1 and Preparation Example 2 were connected in series and incubated with an industrial-grade TMAH aqueous solution (10 wt%, total metal ion content of 2.3 ppm, including potassium, calcium, sodium, magnesium, and iron, and chloride ion content of 72.1 ppm) at 35°C for 1.5 h. -1 The volume hourly space velocity (VHSV) of the TMAH solution is sequentially passed through the front and rear columns of the ion exchange column to remove metal ions and anionic impurities. The TMAH aqueous solution exiting the ion exchange column enters the bubble evaporator, where propylene glycol is added simultaneously. The mass ratio of propylene glycol to tetramethylammonium hydroxide in the TMAH aqueous solution is 4:1. The tower is lined with polytetrafluoroethylene (PTFE), and a high-purity nitrogen microbubble distributor is built into the bottom of the tower. An absolute pressure sensor is installed inside the tower. Preheated high-purity nitrogen (temperature 60℃, purity ≥99.999%) is introduced into the high-purity nitrogen microbubble distributor at a gas velocity of 0.8 m / s. (The high-purity nitrogen microbubble distributor structure: uses PTFE microporous spiral coil, coil specification DN25, outer diameter 25mm, wall thickness 3mm, micropore diameter 1.0mm, and pore spacing 100mm.) The centerline diameter is 960mm, the coil spacing is 100mm, and there are 10 coils in total, with a total unfolded length of approximately 30m. All coils are immersed in the liquid phase at the bottom of the column (one end is closed, and the other end is connected to a high-purity nitrogen preheating pipeline), generating microbubbles of 0.1-0.5mm. The absolute pressure inside the column is controlled at 60kPa, the solution temperature at 55℃, and the material residence time at 120min. The solution in the bubbling evaporator undergoes dehydration and solvent replacement to obtain the TMAH organic solution intermediate. Referring to standard GB / T 606-2003, the water content of the TMAH organic solution intermediate is determined using the Karl Fischer volumetric method, and the water content is 0.46wt%. The TMAH organic solution intermediate is fed into a concentration tank equipped with an online concentration meter. Based on the monitored concentration, propylene glycol is added, and stirring is initiated at 400 rpm for 20 minutes. The solution concentration is then adjusted to 10 wt%. The concentrated solution is then filtered through a three-stage perfluorinated filter series filter. The filtration accuracies of the three perfluorinated filter series filters are 1 μm, 0.1 μm, and 0.05 μm, respectively. The operating temperature is 25°C, and the flow rate is 0.5 m³ / min. 3 / h, after filtration, an electronic-grade tetramethylammonium hydroxide organic solution was obtained. The total metal ion content was 20ppb, the chloride ion content was 49ppb, and the number of particles greater than or equal to 0.1um was ≤100pcs / mL.

[0026] Example 3 The only difference from Example 1 is that the volume hourly space velocity (VHSV) of the industrial-grade TMAH aqueous solution was adjusted to 0.8 h⁻¹ for the ion exchange column. -1 .

[0027] The front and rear columns obtained from Preparation Example 1 and Preparation Example 2 were connected in series, and an industrial-grade TMAH aqueous solution (25 wt%, total metal ion content of 5.4 ppm, including potassium, calcium, sodium, magnesium, iron, and chloride ion content of 254.8 ppm) at 35°C was added at a rate of 0.8 h. -1 The volume hourly space velocity (VHSV) of the TMAH solution is sequentially passed through the front and rear columns of the ion exchange column to remove metal ions and anionic impurities. The TMAH aqueous solution exiting the ion exchange column enters the bubble evaporator, where propylene glycol is added simultaneously. The mass ratio of propylene glycol to tetramethylammonium hydroxide in the TMAH aqueous solution is 4:1. The tower is lined with polytetrafluoroethylene (PTFE), and a high-purity nitrogen microbubble distributor is built into the bottom of the tower. An absolute pressure sensor is installed inside the tower. Preheated high-purity nitrogen (temperature 60℃, purity ≥99.999%) is introduced into the high-purity nitrogen microbubble distributor at a gas velocity of 0.8 m / s. (The high-purity nitrogen microbubble distributor structure: uses PTFE microporous spiral coil, coil specification DN25, outer diameter 25mm, wall thickness 3mm, micropore diameter 1.0mm, and pore spacing 100mm.) The centerline diameter is 960mm, the coil spacing is 100mm, and there are 10 coils in total, with a total unfolded length of approximately 30m. All coils are immersed in the liquid phase at the bottom of the column (one end is closed, and the other end is connected to a high-purity nitrogen preheating pipeline), generating microbubbles of 0.1-0.5mm. The absolute pressure inside the column is controlled at 60kPa, the solution temperature at 55℃, and the material residence time at 45min. The solution in the bubbling evaporator undergoes dehydration and solvent replacement to obtain the TMAH organic solution intermediate. Referring to standard GB / T 606-2003, the water content of the TMAH organic solution intermediate is determined using the Karl Fischer volumetric method, and the water content is 0.41wt%. The TMAH organic solution intermediate is fed into a concentration tank equipped with an online concentration meter. Based on the monitored concentration, propylene glycol is added, and stirring is initiated at 400 rpm for 20 minutes. The solution concentration is then adjusted to 10 wt%. The concentrated solution is then filtered through a three-stage perfluorinated filter series filter. The filtration accuracies of the three perfluorinated filter series filters are 1 μm, 0.1 μm, and 0.05 μm, respectively. The operating temperature is 25°C, and the flow rate is 0.5 m³ / min. 3 / h, after filtration, an electronic-grade tetramethylammonium hydroxide organic solution was obtained. The total metal ion content was 22ppb, the chloride ion content was 46ppb, and the number of particles greater than or equal to 0.1um was ≤100pcs / mL.

[0028] Example 4 The only difference from Example 1 is that the volume hourly space velocity (VHSV) of the industrial-grade TMAH aqueous solution was adjusted to 2.0 h⁻¹ for the ion exchange column. -1 .

[0029] The front and rear columns obtained from Preparation Example 1 and Preparation Example 2 were connected in series and subjected to 2.0 h of industrial-grade TMAH aqueous solution (25 wt%, total metal ion content of 5.4 ppm, including potassium, calcium, sodium, magnesium, iron, and chloride ion content of 254.8 ppm) at 35°C. -1 The volume hourly space velocity (VHSV) of the TMAH solution is sequentially passed through the front and rear columns of the ion exchange column to remove metal ions and anionic impurities. The TMAH aqueous solution exiting the ion exchange column enters the bubble evaporator, where propylene glycol is added simultaneously. The mass ratio of propylene glycol to tetramethylammonium hydroxide in the TMAH aqueous solution is 4:1. The tower is lined with polytetrafluoroethylene (PTFE), and a high-purity nitrogen microbubble distributor is built into the bottom of the tower. An absolute pressure sensor is installed inside the tower. Preheated high-purity nitrogen (temperature 60℃, purity ≥99.999%) is introduced into the high-purity nitrogen microbubble distributor at a gas velocity of 0.8 m / s. (The high-purity nitrogen microbubble distributor structure: uses PTFE microporous spiral coil, coil specification DN25, outer diameter 25mm, wall thickness 3mm, micropore diameter 1.0mm, and pore spacing 100mm.) The centerline diameter is 960mm, the coil spacing is 100mm, and there are 10 coils in total, with a total unfolded length of approximately 30m. All coils are immersed in the liquid phase at the bottom of the column (one end is closed, and the other end is connected to a high-purity nitrogen preheating pipeline), generating microbubbles of 0.1-0.5mm. The absolute pressure inside the column is controlled at 60kPa, the solution temperature at 55℃, and the material residence time at 45min. The solution in the bubbling evaporator undergoes dehydration and solvent replacement to obtain the TMAH organic solution intermediate. Referring to standard GB / T 606-2003, the water content of the TMAH organic solution intermediate is determined using the Karl Fischer volumetric method, and the water content is 0.42wt%. The TMAH organic solution intermediate is fed into a concentration tank equipped with an online concentration meter. Based on the monitored concentration, propylene glycol is added, and stirring is initiated at 400 rpm for 20 minutes. The solution concentration is then adjusted to 10 wt%. The concentrated solution is then filtered through a three-stage perfluorinated filter series filter. The filtration accuracies of the three perfluorinated filter series filters are 1 μm, 0.1 μm, and 0.05 μm, respectively. The operating temperature is 25°C, and the flow rate is 0.5 m³ / min. 3 / h, after filtration, an electronic-grade tetramethylammonium hydroxide organic solution was obtained. The total metal ion content was 29ppb, the chloride ion content was 65ppb, and the number of particles greater than or equal to 0.1um was ≤100pcs / mL.

[0030] Example 5 The only difference from Example 1 is that the gas velocity of high-purity nitrogen is adjusted to 0.5 m / s.

[0031] The front and rear columns obtained from Preparation Example 1 and Preparation Example 2 were connected in series and incubated with an industrial-grade TMAH aqueous solution (25 wt%, total metal ion content of 5.4 ppm, including potassium, calcium, sodium, magnesium, iron, and chloride ion content of 254.8 ppm) at 35°C for 1.5 h. -1 The volume hourly space velocity (VHSV) of the TMAH solution is sequentially passed through the front and rear columns of the ion exchange column to remove metal ions and anionic impurities. The TMAH aqueous solution exiting the ion exchange column enters the bubble evaporator, where propylene glycol is added simultaneously. The mass ratio of propylene glycol to tetramethylammonium hydroxide in the TMAH aqueous solution is 4:1. The tower is lined with polytetrafluoroethylene (PTFE), and a high-purity nitrogen microbubble distributor is built into the bottom of the tower. An absolute pressure sensor is installed inside the tower. Preheated high-purity nitrogen (temperature 60℃, purity ≥99.999%) is introduced into the high-purity nitrogen microbubble distributor at a gas velocity of 0.5 m / s. (The high-purity nitrogen microbubble distributor structure: uses PTFE microporous spiral coil, coil specification DN25, outer diameter 25mm, wall thickness 3mm, micropore diameter 1.0mm, and pore spacing 100mm.) The centerline diameter is 960mm, the coil spacing is 100mm, and there are 10 coils in total, with a total unfolded length of approximately 30m. All coils are immersed in the liquid phase at the bottom of the column (one end is closed, and the other end is connected to a high-purity nitrogen preheating pipeline), generating microbubbles of 0.1-0.5mm. The absolute pressure inside the column is controlled at 60kPa, the solution temperature at 55℃, and the material residence time at 45min. The solution in the bubbling evaporator undergoes dehydration and solvent replacement to obtain the TMAH organic solution intermediate. Referring to standard GB / T 606-2003, the water content of the TMAH organic solution intermediate is determined using the Karl Fischer volumetric method, and the water content is 0.45wt%. The TMAH organic solution intermediate is fed into a concentration tank equipped with an online concentration meter. Based on the monitored concentration, propylene glycol is added, and stirring is initiated at 400 rpm for 20 minutes. The solution concentration is then adjusted to 10 wt%. The concentrated solution is then filtered through a three-stage perfluorinated filter series filter. The filtration accuracies of the three perfluorinated filter series filters are 1 μm, 0.1 μm, and 0.05 μm, respectively. The operating temperature is 25°C, and the flow rate is 0.5 m³ / min. 3 / h, after filtration, an electronic-grade tetramethylammonium hydroxide organic solution was obtained. The total metal ion content was 25ppb, the chloride ion content was 53ppb, and the number of particles greater than or equal to 0.1um was ≤100pcs / mL.

[0032] Example 6 The only difference from Example 1 is that the gas velocity of high-purity nitrogen is adjusted to 1.0 m / s.

[0033] The front and rear columns obtained from Preparation Example 1 and Preparation Example 2 were connected in series and incubated with an industrial-grade TMAH aqueous solution (25 wt%, total metal ion content of 5.4 ppm, including potassium, calcium, sodium, magnesium, iron, and chloride ion content of 254.8 ppm) at 35°C for 1.5 h. -1 The volume hourly space velocity (VHSV) of the TMAH solution is sequentially passed through the front and rear columns of the ion exchange column to remove metal ions and anionic impurities. The TMAH aqueous solution exiting the ion exchange column enters the bubble evaporator, where propylene glycol is added simultaneously. The mass ratio of propylene glycol to tetramethylammonium hydroxide in the TMAH aqueous solution is 4:1. The tower is lined with polytetrafluoroethylene (PTFE), and a high-purity nitrogen microbubble distributor is built into the bottom of the tower. An absolute pressure sensor is installed inside the tower. Preheated high-purity nitrogen (temperature 60℃, purity ≥99.999%) is introduced into the high-purity nitrogen microbubble distributor at a velocity of 1.0 m / s. (The high-purity nitrogen microbubble distributor structure: uses PTFE microporous spiral coil, coil specification DN25, outer diameter 25mm, wall thickness 3mm, micropore diameter 1.0mm, and pore spacing 100mm.) The centerline diameter is 960mm, the coil spacing is 100mm, and there are 10 coils in total, with a total unfolded length of approximately 30m. All coils are immersed in the liquid phase at the bottom of the column (one end is closed, and the other end is connected to a high-purity nitrogen preheating pipeline), generating microbubbles of 0.1-0.5mm. The absolute pressure inside the column is controlled at 60kPa, the solution temperature at 55℃, and the material residence time at 45min. The solution in the bubbling evaporator undergoes dehydration and solvent replacement to obtain the TMAH organic solution intermediate. Referring to standard GB / T 606-2003, the water content of the TMAH organic solution intermediate is determined using the Karl Fischer volumetric method, and the water content is 0.44wt%. The TMAH organic solution intermediate is fed into a concentration tank equipped with an online concentration meter. Based on the monitored concentration, propylene glycol is added, and stirring is initiated at 400 rpm for 20 minutes. The solution concentration is then adjusted to 10 wt%. The concentrated solution is then filtered through a three-stage perfluorinated filter series filter. The filtration accuracies of the three perfluorinated filter series filters are 1 μm, 0.1 μm, and 0.05 μm, respectively. The operating temperature is 25°C, and the flow rate is 0.5 m³ / min. 3 / h, after filtration, an electronic-grade tetramethylammonium hydroxide organic solution was obtained. The total metal ion content was 26ppb, the chloride ion content was 55ppb, and the number of particles greater than or equal to 0.1um was ≤100pcs / mL.

[0034] Example 7 The only difference from Example 1 is that the mass ratio of propylene glycol to tetramethylammonium hydroxide in the TMAH aqueous solution is adjusted to 3:1, the absolute pressure in the control tower is 40 kPa, and the solution temperature is 50°C.

[0035] The front and rear columns obtained from Preparation Example 1 and Preparation Example 2 were connected in series and incubated with an industrial-grade TMAH aqueous solution (25 wt%, total metal ion content of 5.4 ppm, including potassium, calcium, sodium, magnesium, iron, and chloride ion content of 254.8 ppm) at 35°C for 1.5 h. -1 The volume hourly space velocity (VHSV) of the TMAH solution sequentially passes through the front and rear columns of the ion exchange column to remove metal ions and anionic impurities. The TMAH aqueous solution exiting the ion exchange column enters the bubble evaporator, where propylene glycol is added simultaneously at a mass ratio of propylene glycol to tetramethylammonium hydroxide in the TMAH aqueous solution of 3:1. The tower is lined with polytetrafluoroethylene (PTFE), and a high-purity nitrogen microbubble distributor is built into the bottom of the tower. An absolute pressure sensor is installed inside the tower. Preheated high-purity nitrogen (temperature 60℃, purity ≥99.999%) is introduced into the high-purity nitrogen microbubble distributor at a velocity of 0.8 m / s. (The high-purity nitrogen microbubble distributor structure: uses PTFE microporous spiral coil, coil specification DN25, outer diameter 25mm, wall thickness 3mm, micropore diameter 1.0mm, and pore spacing 10). 0mm. The coil centerline diameter is 960mm, the coil spacing is 100mm, a total of 10 coils, and the total unfolded length is approximately 30m. All coils are immersed in the liquid phase at the bottom of the tower (one end is closed, and the other end is connected to a high-purity nitrogen preheating pipeline), generating microbubbles of 0.1-0.5mm. The absolute pressure inside the tower is controlled at 40kPa, the solution temperature at 50℃, and the material residence time at 45min. The solution in the bubbling evaporator completes dehydration and solvent replacement to obtain TMAH organic solution intermediate. Referring to standard GB / T 606-2003, the water content of TMAH organic solution intermediate is determined by Karl Fischer volumetric method, and the water content is 0.48wt%. The TMAH organic solution intermediate is fed into a concentration tank equipped with an online concentration meter. Based on the monitored concentration, propylene glycol is added, and stirring is initiated at 400 rpm for 20 minutes. The solution concentration is then adjusted to 10 wt%. The concentrated solution is then filtered through a three-stage perfluorinated filter series filter. The filtration accuracies of the three perfluorinated filter series filters are 1 μm, 0.1 μm, and 0.05 μm, respectively. The operating temperature is 25°C, and the flow rate is 0.5 m³ / min. 3 / h, after filtration, an electronic-grade tetramethylammonium hydroxide organic solution was obtained. The total metal ion content was 24ppb, the chloride ion content was 52ppb, and the number of particles greater than or equal to 0.1um was ≤100pcs / mL.

[0036] Example 8 The only difference from Example 1 is that the mass ratio of propylene glycol to tetramethylammonium hydroxide in the TMAH aqueous solution is adjusted to 5:1, the absolute pressure in the control tower is 80 kPa, and the solution temperature is 60°C.

[0037] The front and rear columns obtained from Preparation Example 1 and Preparation Example 2 were connected in series and incubated with an industrial-grade TMAH aqueous solution (25 wt%, total metal ion content of 5.4 ppm, including potassium, calcium, sodium, magnesium, iron, and chloride ion content of 254.8 ppm) at 35°C for 1.5 h. -1 The volume hourly space velocity (VHSV) of the TMAH solution is sequentially passed through the front and rear columns of the ion exchange column to remove metal ions and anionic impurities. The TMAH aqueous solution exiting the ion exchange column enters the bubble evaporator, where propylene glycol is added simultaneously. The mass ratio of propylene glycol to tetramethylammonium hydroxide in the TMAH aqueous solution is 5:1. The tower is lined with polytetrafluoroethylene (PTFE), and a high-purity nitrogen microbubble distributor is built into the bottom of the tower. An absolute pressure sensor is installed inside the tower. Preheated high-purity nitrogen (temperature 60℃, purity ≥99.999%) is introduced into the high-purity nitrogen microbubble distributor at a gas velocity of 0.8 m / s. (The high-purity nitrogen microbubble distributor structure: uses PTFE microporous spiral coil, coil specification DN25, outer diameter 25mm, wall thickness 3mm, micropore diameter 1.0mm, and pore spacing 100mm.) The centerline diameter is 960mm, the coil spacing is 100mm, and there are 10 coils in total, with a total unfolded length of approximately 30m. All coils are immersed in the liquid phase at the bottom of the column (one end is closed, and the other end is connected to a high-purity nitrogen preheating pipeline), generating microbubbles of 0.1-0.5mm. The absolute pressure inside the column is controlled at 80kPa, the solution temperature at 60℃, and the material residence time at 45min. The solution in the bubbling evaporator undergoes dehydration and solvent replacement to obtain the TMAH organic solution intermediate. Referring to standard GB / T 606-2003, the water content of the TMAH organic solution intermediate is determined using the Karl Fischer volumetric method, and the water content is 0.39wt%. The TMAH organic solution intermediate is fed into a concentration tank equipped with an online concentration meter. Based on the monitored concentration, propylene glycol is added, and stirring is initiated at 400 rpm for 20 minutes. The solution concentration is then adjusted to 10 wt%. The concentrated solution is then filtered through a three-stage perfluorinated filter series filter. The filtration accuracies of the three perfluorinated filter series filters are 1 μm, 0.1 μm, and 0.05 μm, respectively. The operating temperature is 25°C, and the flow rate is 0.5 m³ / min. 3 / h, after filtration, an electronic-grade tetramethylammonium hydroxide organic solution was obtained. The total metal ion content was 27ppb, the chloride ion content was 55ppb, and the number of particles greater than or equal to 0.1um was ≤100pcs / mL.

[0038] Comparative Example 1 The only difference from Example 1 is that a hydrogen-form strong acid cation exchange resin is used instead of a tetramethylammonium-form strong acid cation exchange resin.

[0039] The washed strong acid cation exchange resin (Amberlyst® 15) was packed into a front column with an inner diameter of 5.5 cm, a height of 78 cm, and a diameter-to-height ratio of 1:14. 4 wt% hydrochloric acid was slowly flowed through the resin, with the amount being 4 times the resin volume and the flow rate being 1.5 times the bed volume per hour. After the hydrochloric acid was completely introduced, the resin was soaked for 5 hours to remove the hydrochloric acid. The resin was then rinsed with ultrapure water until the effluent was neutral.

[0040] The front and rear columns obtained in this comparative example and Preparation Example 2 were connected in series and in an industrial-grade TMAH aqueous solution (25 wt%, total metal ion content of 5.4 ppm, including potassium, calcium, sodium, magnesium, iron, and chloride ion content of 254.8 ppm) at 35°C for 1.5 h. -1The volume hourly space velocity (VHSV) of the TMAH solution is sequentially passed through the front and rear columns of the ion exchange column to remove metal ions and anionic impurities. The TMAH aqueous solution exiting the ion exchange column enters the bubble evaporator, where propylene glycol is added simultaneously. The mass ratio of propylene glycol to tetramethylammonium hydroxide in the TMAH aqueous solution is 4:1. The tower is lined with polytetrafluoroethylene (PTFE), and a high-purity nitrogen microbubble distributor is built into the bottom of the tower. An absolute pressure sensor is installed inside the tower. Preheated high-purity nitrogen (temperature 60℃, purity ≥99.999%) is introduced into the high-purity nitrogen microbubble distributor at a gas velocity of 0.8 m / s. (The high-purity nitrogen microbubble distributor structure: uses PTFE microporous spiral coil, coil specification DN25, outer diameter 25mm, wall thickness 3mm, micropore diameter 1.0mm, and pore spacing 100mm.) The centerline diameter is 960mm, the coil spacing is 100mm, and there are 10 coils in total, with a total unfolded length of approximately 30m. All coils are immersed in the liquid phase at the bottom of the column (one end is closed, and the other end is connected to a high-purity nitrogen preheating pipeline), generating microbubbles of 0.1-0.5mm. The absolute pressure inside the column is controlled at 80kPa, the solution temperature at 55℃, and the material residence time at 45min. The solution in the bubbling evaporator undergoes dehydration and solvent replacement to obtain the TMAH organic solution intermediate. Referring to standard GB / T 606-2003, the water content of the TMAH organic solution intermediate is determined using the Karl Fischer volumetric method, and the water content is 0.43wt%. The TMAH organic solution intermediate is fed into a concentration tank equipped with an online concentration meter. Based on the monitored concentration, propylene glycol is added, and stirring is initiated at 400 rpm for 20 minutes. The solution concentration is then adjusted to 10 wt%. The concentrated solution is then filtered through a three-stage perfluorinated filter series filter. The filtration accuracies of the three perfluorinated filter series filters are 1 μm, 0.1 μm, and 0.05 μm, respectively. The operating temperature is 25°C, and the flow rate is 0.5 m³ / min. 3 / h, after filtration, an electronic-grade tetramethylammonium hydroxide organic solution was obtained. The total metal ion content was 36ppb, the chloride ion content was 60ppb, and the number of particles greater than or equal to 0.1um was ≤100pcs / mL.

[0041] Comparative Example 2 The only difference from Example 1 is that nitrogen bubbling is not installed in the evaporation tower.

[0042] The front and rear columns obtained from Preparation Example 1 and Preparation Example 2 were connected in series and incubated with an industrial-grade TMAH aqueous solution (25 wt%, total metal ion content of 5.4 ppm, including potassium, calcium, sodium, magnesium, iron, and chloride ion content of 254.8 ppm) at 35°C for 1.5 h. -1The volume hourly space velocity (VHSV) of the TMAH solution is sequentially passed through the front and rear columns of an ion exchange column to remove metal ions and anionic impurities. The TMAH aqueous solution exiting the ion exchange column enters a bubble evaporator, where propylene glycol is added simultaneously at a mass ratio of 4:1 to tetramethylammonium hydroxide in the TMAH aqueous solution. The column is lined with polytetrafluoroethylene (PTFE), and a high-purity nitrogen microbubble distributor (without nitrogen delivery) is installed at the bottom. An absolute pressure sensor is installed inside the column to control the absolute pressure at 80 kPa, the solution temperature at 55°C, and the material residence time at 45 min. The solution undergoes dehydration and solvent replacement in the bubble evaporator to obtain the TMAH organic solution intermediate. Referring to standard GB / T 606-2003, the water content of the TMAH organic solution intermediate is determined using the Karl Fischer volumetric method, and the water content is 0.74 wt%. The TMAH organic solution intermediate is fed into a concentration tank equipped with an online concentration meter. Based on the monitored concentration, propylene glycol is added, and stirring is initiated at 400 rpm for 20 minutes. The solution concentration is then adjusted to 10 wt%. The concentrated solution is then filtered through a three-stage perfluorinated filter series filter. The filtration accuracies of the three perfluorinated filter series filters are 1 μm, 0.1 μm, and 0.05 μm, respectively. The operating temperature is 25°C, and the flow rate is 0.5 m³ / min. 3 / h, after filtration, an electronic-grade tetramethylammonium hydroxide organic solution was obtained. The total metal ion content was 30ppb, the chloride ion content was 59ppb, and the number of particles greater than or equal to 0.1um was ≤100pcs / mL.

[0043] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0044] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A production process for an electronic-grade tetramethylammonium hydroxide organic solution, characterized in that, Includes the following steps: S1. Industrial-grade TMAH aqueous solution is passed through ion exchange columns connected in series with cation and anion columns to remove metal ions and anion impurities. S2. The TMAH aqueous solution after ion exchange treatment enters the bubble evaporator, propylene glycol is added simultaneously, high-purity nitrogen gas is bubbled into the liquid phase to generate microbubbles, negative pressure evaporation and dehydration are carried out to form TMAH organic solution intermediate. S3 and TMAH organic solution intermediates are introduced into the concentration tank, and the concentration is monitored online. Propylene glycol is added and mixed according to the TMAH concentration requirements to adjust the concentration. S4. The concentrated solution is filtered through a multi-stage filter cartridge to obtain an electronic grade tetramethylammonium hydroxide organic solution.

2. The production process of an electronic-grade tetramethylammonium hydroxide organic solution according to claim 1, characterized in that, The cation exchange column is filled with a tetramethylammonium type strong acid cation exchange resin.

3. The production process of an electronic-grade tetramethylammonium hydroxide organic solution according to claim 2, characterized in that, The preparation steps of the tetramethylammonium type strong acid cation exchange resin are as follows: After packing the strongly acidic cation exchange resin column, slowly flow 4-5 wt% hydrochloric acid through the resin, using 3-4 times the resin volume at a flow rate of 1.5 times the bed volume per hour. After the hydrochloric acid is completely introduced, soak for 4-6 hours to remove the hydrochloric acid. Rinse the resin with ultrapure water until the effluent is neutral. After stopping the rinsing, slowly flow 4-5 wt% electronic-grade TMAH aqueous solution through the resin, using 3-4 times the resin volume at a flow rate of 1.5 times the bed volume per hour. After the electronic-grade TMAH aqueous solution is completely introduced, soak for 4-6 hours and rinse with ultrapure water until the effluent is neutral.

4. The production process of an electronic-grade tetramethylammonium hydroxide organic solution according to claim 1, characterized in that, The anion exchange column is packed with OH - A type of strongly basic anion exchange resin.

5. The production process of an electronic-grade tetramethylammonium hydroxide organic solution according to claim 4, characterized in that, The OH - The preparation steps of the strong basic anion exchange resin are as follows: After packing the strongly basic anion exchange resin column, slowly flow 4-5 wt% hydrochloric acid through the resin, using 3-4 times the resin volume at a flow rate of 1.5 times the bed volume per hour. After the hydrochloric acid is completely introduced, soak for 4-6 hours to remove the hydrochloric acid. Rinse the resin with ultrapure water until the effluent is neutral. After stopping the rinsing, slowly flow 4-5 wt% sodium hydroxide solution through the resin, using 3-4 times the resin volume at a flow rate of 1.5 times the bed volume per hour. After the sodium hydroxide solution is completely introduced, soak for 4-6 hours and rinse with ultrapure water until the effluent is neutral.

6. The production process of an electronic-grade tetramethylammonium hydroxide organic solution according to claim 1, characterized in that, The volume hourly space velocity (HSV) of the industrial-grade TMAH aqueous solution passing through a series ion exchange column is 0.8-2.0 h⁻¹. -1 The temperature of industrial-grade TMAH aqueous solution is 25-45℃.

7. The production process of an electronic-grade tetramethylammonium hydroxide organic solution according to claim 1, characterized in that, The absolute pressure inside the bubbling evaporator is 40-100 kPa, and the solution temperature is 50-60℃; in step S2, the mass ratio of propylene glycol to tetramethylammonium hydroxide in the TMAH aqueous solution is 3:1-5:

1. The high-purity nitrogen gas has a temperature of 60-70℃, a purity of ≥99.999%, and a gas velocity of 0.5-1.0m / s; The water content in the TMAH organic solution intermediate is <0.5wt%.

8. The production process of an electronic-grade tetramethylammonium hydroxide organic solution according to claim 1, characterized in that, The multi-stage filter cartridge uses a three-stage perfluorinated filter cartridge in series, with filtration accuracies of 1μm, 0.1μm and 0.05μm respectively, and an operating temperature of 20-30℃.

9. An electronic-grade tetramethylammonium hydroxide organic solution, characterized in that, The electronic grade tetramethylammonium hydroxide organic solution is produced using the production process described in any one of claims 1-8, wherein the concentration is 10-20 wt%, the total metal ion content is ≤30 ppb, the chloride ion content is ≤100 ppb, and the number of particles greater than or equal to 0.1 μm is ≤100 pcs / mL.

10. An application of an electronic-grade tetramethylammonium hydroxide organic solution, characterized in that, The electronic-grade tetramethylammonium hydroxide organic solution as described in claim 9 can be used to prepare photoresist cleaning agents.