Method for producing TiO2 powder and TiO2 powder produced thereby
The method recycles NH3 and TiCl4 residues to produce TiO2 powder with controlled crystalline structure and size, addressing resource wastage and enhancing photocatalytic activity in the visible light region.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- キムジ ソク
- Filing Date
- 2024-12-06
- Publication Date
- 2026-06-18
AI Technical Summary
Existing technologies fail to effectively recycle residual NH3 and TiCl4 discharged during Ti-N layer formation in semiconductor manufacturing, leading to resource wastage, while TiO2 materials lack effective photocatalytic activity in the visible light region.
A method to produce TiO2 powder by capturing and dissolving NH3 and TiCl4 residues in a solvent, forming TiO2 and NH4Cl, and separating the TiO2 powder, which can be further processed to achieve specific crystal structures and sizes for enhanced photocatalytic performance.
Recycles residual NH3 and TiCl4, producing TiO2 powder with controlled crystalline structure and size, enabling effective photocatalytic activity in the visible light region and reducing waste.
Smart Images
Figure 2026099615000001_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a method for producing TiO2 powder and TiO2 powder produced thereby.
Background Art
[0002] In the case of photocatalysts, basically, safety must be ensured, and in order to exhibit their functions, they must have the ability to absorb light and oxidize other substances. However, although TiO2 is mainly used as a white paint, not only does it exhibit suitable properties for photocatalysts, but if it is mixed with other dyes or colored organic substances to perform the photocatalytic role, it can also perform the photocatalytic role as light in the visible light region.
[0003] On the other hand, in the Ti-N layer formation semiconductor manufacturing process, NH3 and TiCl3 are reacted on the wafer to form a Ti-N layer. However, NH3 and TiCl4 actually used for forming the Ti-N layer only account for about 10% of the supply amount, and the remaining 90% is discharged and discarded. Therefore, it is necessary to recover the residual NH3 and TiCl4 discharged in terms of resource recycling, but the fact is that no technology that can solve this problem has been proposed.
Prior Art Documents
Patent Documents
[0004]
Patent Document 1
Patent Document 2
Patent Document 3
Summary of the Invention
[0005] The present invention aims to solve the problems of the prior art described above, and the objective of the present invention is to provide a method for producing TiO2 powder from a mixture discharged when NH3 and TiCl4 are reacted on a wafer to form a Ti-N layer. [Means for solving the problem]
[0006] One embodiment of the present invention for producing TiO2 powder to achieve the aforementioned objectives includes the steps of: capturing NH3 and TiCl4 in the residue after TiN layer formation; dissolving the NH3 and TiCl4 in a solvent to produce a mixture; acquiring TiO2 and NH4Cl from the mixture; and separating TiO2 powder from the acquired TiO2 and NH4Cl.
[0007] In one embodiment of the present invention, the TiO2 powder is nanoparticles. In one embodiment of the present invention, the TiO2 powder has a size of 10 nm to 20 nm. In one embodiment of the present invention, the crystalline state of the TiO2 powder is anatase and a mixture of anatase and rutile. In one embodiment of the present invention, the molar ratio of the solvent to NH3 and TiCl4 is 1:0.01 to 1:0.13 during the preparation of the mixture. In one embodiment of the present invention, the pH range is -0.02 to 1 during the stage in which the mixture is produced. In one embodiment of the present invention, the solvent is selected from the group consisting of nitric acid, ammonia, hydrogen peroxide, hydrochloric acid, and combinations thereof.
[0008] In one embodiment of the present invention, during the preparation of the mixture, the NH3 and TiCl4 are dissolved in the solvent and reacted under temperature conditions of 25°C to 350°C.
[0009] In one embodiment of the present invention, during the preparation of the mixture, the NH3 and TiCl4 are dissolved in the solvent and reacted under pressure conditions of 1 bar to 10 bar.
[0010] In one embodiment of the present invention, at the stage in which TiO2 and NH4Cl are acquired, the TiO2 and NH4Cl are acquired from the mixture under temperature conditions of 200°C to 1,000°C.
[0011] One embodiment of the present invention further includes the step of additionally heat-treating the acquired TiO2 powder.
[0012] In one embodiment of the present invention, during the additional heat treatment of the TiO2 powder, the acquired TiO2 powder is heat-treated under temperature conditions of 200°C to 1,000°C.
[0013] In another embodiment of the method for producing TiO2 powder according to the embodiments of the present invention, TiO2 and NH4Cl are obtained from a mixture produced by dissolving NH3 and TiCl4, which are trapped by the residue after TiN layer formation, in a solvent, and then TiO2 powder is separated from there.
[0014] One form of TiO2 powder according to the embodiment of the present invention is produced by any one of the methods of claims 1 to 13. [Effects of the Invention]
[0015] In the method for producing TiO2 powder according to the embodiment of the present invention, and in the TiO2 powder produced thereby, TiO2 and NH4Cl are obtained from residual NH3 and TiCl4 that are discharged without reacting during the process of forming the Ti-N layer on the wafer, and TiO2 powder is separated from these. Therefore, according to the embodiment of the present invention, it becomes possible to produce TiO2 powder by recycling the discharged residual NH3 and TiCl4. [Brief explanation of the drawing]
[0016] [Figure 1]This is a SEM image showing the size of TiO2 powder particles. [Figure 2] Similarly, this is a SEM image showing the size of TiO2 powder particles. [Figure 3] Similarly, this is a SEM image showing the size of TiO2 powder particles. [Figure 4] Similarly, this is a SEM image showing the size of TiO2 powder particles. [Figure 5] Similarly, this is a SEM image showing the size of TiO2 powder particles. [Figure 6] This is a graph showing the size of TiO2 powder particles according to temperature. [Figure 7] This is a graph showing the ratio of the crystal structures of anatase and the mixed state of anatase and rutile by pH adjustment. [Figure 8] This is a TiO2 powder image according to temperature and time. [Figure 9] This is a graph showing the difference in solubility according to temperature.
Mode for Carrying Out the Invention
[0017] Hereinafter, the TiO2 powder manufacturing method according to an embodiment of the present invention will be described in more detail with reference to the attached drawings.
[0018] The method for manufacturing TiO2 powder according to an embodiment of the present invention for achieving the above-described object includes the steps of capturing NH3 and TiCl4 remaining after the formation of the Ti-N layer, dissolving the NH3 and TiCl4 in a solvent to produce a mixture, reacting the mixture to obtain TiO2 and NH4Cl, and separating the obtained TiO2 and NH4Cl to obtain TiO2 powder.
[0019] In the Ti-N layer formation semiconductor manufacturing process, NH3 and TiCl4 are reacted on a wafer to form a Ti-N layer. NH3 and TiCl4 discharged after layer formation are captured to produce TiO2 powder.
[0020] In the process of producing the aforementioned mixture, the solvent can be used to adjust the acidity of the NH3 and TiCl4 mixture between -0.02 and 1, and to adjust the ratio of anatase or a mixture of anatase and rutile in the resulting TiO2 crystal structure. In particular, the hue of the TiO2 powder obtained can be adjusted by heat-treating the rutile-structured TiO2 in a temperature range of 200°C to 800°C. If the temperature range is 1,000°C or higher, the final acquired TiO2 powder structure can be changed to a rutile structure. Furthermore, the molar ratio of NH3 and TiCl4 to the solvent can be adjusted from 0.01:1 to 0.13:1, and is selected from the group consisting of nitric acid, ammonia, hydrogen peroxide, hydrochloric acid, and combinations thereof.
[0021] The step of producing the aforementioned mixture can be carried out by utilizing a hydration reaction or a high-pressure reaction for solid-liquid separation. The hydration reaction can be carried out at temperatures between 25°C and 100°C. The size of the TiO2 particles produced in the aforementioned room temperature range is in the range of 2 nm to 10 nm. In fact, the size of the particles produced in the NH4Cl solution is very small because NH4Cl hinders particle growth. When TiO2 is produced, the size of the crystal grains remains nanoscale. However, depending on the heating temperature, it can be produced by forming aggregates and filtering them. Therefore, if aggregates are formed to a certain size, and then filtered and pulverized to produce particles, the particle size can be formed to be around 10 nm. The ammonia produced in this invention can hinder the growth of TiO2 particles and is therefore recovered in NH4Cl.
[0022] On the other hand, a high-pressure reaction can be used in a method that aggregates the particles produced by the hydration reaction, which are very small in size, to facilitate filtering. The temperature range for the high-pressure reaction may be 25°C to 350°C, and the reaction can be carried out at a pressure range of 1 bar to 10 bar. TiO2 powder produced with a larger particle size by adjusting the temperature and pressure conditions as described above can be filtered for solid-liquid separation.
[0023] By heat-treating a mixture subjected to a hydration reaction or high-pressure reaction at a temperature of 300°C to 1,100°C for 10 to 120 minutes, the particle size can be adjusted to 10 nm to 500 nm.
[0024] Furthermore, a yellow dye can be produced by further heat treatment of TiO2 having a 100% rutile crystal structure from 300°C to 1,000°C. In particular, a variety of yellow dye concentrations can be obtained depending on the temperature range. The TiO2 powder produced by the above manufacturing method can be obtained as nanoparticles, and the size of the nanoparticle powder can be in the range of 10 nm to 20 nm.
[0025] The following describes examples of manufacturing and experimental procedures of the present invention. However, these examples are intended to more specifically illustrate the structure and effects of the present invention, and the scope of the present invention is not limited thereto.
[0026] Examples <Production example 1: TiO2 powder production> After the formation of the TiN layer, the NH3 and TiCl4 discharged from the reactor were condensed in a trap and collected as a mixture. Ultrapure water was added as a solvent to the condensed mixture of NH3 and TiCl4 in a molar ratio of 1:0.13 to 0.01 and mixed. The mixture was heated at 45°C for 2 hours to dissolve. The dissolved mixture was then used to form TiO2 and NH4Cl at room temperature and pressure. The TiO2 and NH4Cl formed at this time were primarily separated using a filter, and then the TiO2 powder and NH4Cl were subjected to secondary solid-liquid separation.
[0027] <Production example 2: TiO2 powder production> The same manufacturing procedure as in Example 1 was followed, but the heating conditions were changed to 70°C for 1.5 hours.
[0028] <Production example 3: TiO2 powder production> The same manufacturing procedure as in Example 1 was followed, but the heating conditions were changed to 90°C for 2 hours.
[0029] <Production example 4: TiO2 powder production> The manufacturing process was the same as in Example 1, but the heating conditions were changed: primary heating was performed at 70°C for 1 hour and 20 minutes, followed by secondary heating at 90°C for 2 hours.
[0030] <Production example 5: TiO2 powder production> The manufacturing process was the same as in Example 1, but the heating conditions were changed: primary heating was performed at 50°C for 1 hour and 20 minutes, followed by secondary heating at 90°C for 2 hours.
[0031] <Production example 6: TiO2 powder production> The manufacturing process was the same as in Example 1, but the heating conditions were changed to 800°C for 0.5 hours.
[0032] <Production example 7: TiO2 powder production> The manufacturing process was the same as in Example 1, but the heating conditions were changed to 600°C for 1 hour.
[0033] <Manufacturing Example 8: Production of TiO2 Powder under High Temperature and High Pressure> After the formation of the TiN layer, the NH3 and TiCl4 discharged from the reactor were condensed in a trap and collected as a mixture. Ultrapure water was added as a solvent to the condensed mixture of NH3 and TiCl4 in a molar ratio of 1:0.01 to 0.13 and mixed. The mixture was reacted at 150°C and 4 bar to dissolve. The dissolved mixture was heated at 150°C and 4 bar for 180 minutes to form and obtain TiO2 and NH4Cl. The TiO2 and NH4Cl formed at this time were primarily separated using a filter, and then the TiO2 powder and NH4Cl were subjected to secondary solid-liquid separation.
[0034] <Manufacturing Example 9: Changes in TiO2 Powder Particle Size Due to Heat Treatment Conditions> After the TiN layer was formed, the mixture was discharged from the reactor and condensed in a trap to collect the NH3 and TiCl4 as a mixture. Ultrapure water was added as a solvent in a molar ratio of 1:0.01 to 0.13 and mixed with the condensed mixture of NH3 and TiCl4. The conditions for acquiring TiO2 and NH4Cl were the same as those for Examples 1 to 3 and Examples 6 and 7. The acquired TiO2 was heated for 20 to 180 minutes under the temperature conditions shown in Table 1 below to adjust the particle size of the TiO2.
[0035] [Table 1]
[0036] <Manufacturing Example 10: Production of TiO2 powder having a rutile crystal structure> After the formation of the TiN layer, the NH3 and TiCl4 discharged from the reactor were condensed in a trap and collected as a mixture. Ultrapure water was added as a solvent to the condensed mixture of NH3 and TiCl4 in a molar ratio of 1:0.1 to 0.25 and mixed. The mixture was reacted at 25 to 130°C and 1 to 4 bar for 30 to 180 minutes to obtain TiO2 and NH4Cl. Then, the formed TiO2 was separated from the NH4Cl using a filter, and the TiO2 powder was subjected to solid-liquid separation. The obtained TiO2 powder was further heat-treated at a temperature range of 300 to 800°C for 30 to 120 minutes to produce yellow dyes of various concentrations.
[0037] <Manufacturing Example 11: Production of TiO2 powder having rutile and anatase crystal structures> After the formation of the TiN layer, the NH3 and TiCl4 discharged from the reactor were condensed in a trap and collected as a mixture. Ultrapure water was added to the condensed mixture of NH3 and TiCl4 in a molar ratio of 0.02:1 and mixed. The mixture was heated at 25 to 130°C and 1 to 3 bar for 120 minutes to obtain TiO2 and NH4Cl. The formed TiO2 and NH4Cl were primarily separated using a filter, and then the TiO2 powder and NH4Cl were subjected to secondary solid-liquid separation. The obtained TiO2 powder was further heat-treated at a temperature range of 200 to 1,000°C for 30 to 120 minutes to stabilize the crystal structure and control the mixed crystal structure of anatase and rutile.
[0038] Table 2 below shows the results of analyzing the size (nm) of X-RD particles using the Scherrer Equation for manufacturing examples 1 to 5.
[0039] [Table 2]
[0040] In fact, the particles produced in the NH4Cl solution are very small. This is because NH4Cl inhibits particle growth. Therefore, when aggregates are formed to a certain size and then crushed to produce individual particles, the particle size is approximately 10 nm.
[0041] Figures 1 to 5 are SEM images showing the size of TiO2 powder particles obtained by the heat treatment temperature in Production Example 9. As shown in Figure 6, it was possible to adjust the size of the powder particles by controlling the heat treatment temperature during production.
[0042] Figure 7 is a graph showing the proportion of anatase and mixed anatase-rutile crystalline structures under pH adjustment in production examples 10 and 11. Different crystalline structures could be obtained by adjusting the pH by adding a solvent.
[0043] Figure 8 shows TiO2 powder with a 100% rutile structure, obtained from Production Example 10, which was heat-treated at temperatures ranging from 200°C to 1,000°C and for 10 to 120 minutes, with the temperature and time adjusted accordingly. By adjusting the temperature and time, it was possible to produce TiO2 powder as a yellow dye of various concentrations.
[0044] Figure 9 is a graph showing the difference in solubility with temperature. It was found that solubility increases as the temperature increases.
Claims
1. After TiN layer formation, the remaining material is NH ３ And the stage in which TiCl4 is captured, The solvent is the NH ３ and TiCl ４ The stage in which the mixture is produced by dissolving it, From the aforementioned mixture, TiO 2 and NH ４ The stage at which Cl is acquired, and The acquired TiO 2 and NH ４ Cl and LoO 2 The step in which the powder is separated includes A method for producing TiO characterized by 2 powder.
2. The aforementioned CoO 2 The powder consists of nanoparticles. The TiO described in claim 1 2 A method for producing powder.
3. The aforementioned CoO 2 The powder consists of nanoparticles with a size of 10 nm to 20 nm. The TiO described in claim 1 2 A method for producing powder.
4. The aforementioned CoO 2 The powdered crystalline form is anatase and a mixture of anatase and rutile. The TiO described in claim 1 2 A method for producing powder.
5. In the process of producing the aforementioned mixture, The solvent and NH ３ and TiCl ４ The molar ratio is between 1:0.01 and 1:0.
13. The TiO described in claim 1 2 A method for producing powder.
6. In the process of producing the aforementioned mixture, The pH range is -0.02 to 1. The TiO described in claim 1 2 A method for producing powder.
7. The solvent is selected from the group consisting of nitric acid, ammonia, hydrogen peroxide, hydrochloric acid, and combinations thereof. The TiO described in claim 1 2 A method for producing powder.
8. In the process of producing the aforementioned mixture, The NH ３ and TiCl ４ are dissolved in the solvent and reacted under temperature conditions of 25°C to 350°C The TiO described in claim 1 2 A method for producing powder.
9. In the process of producing the aforementioned mixture, Said NH ３ and TiCl ４ It is dissolved in the solvent and reacted under pressure conditions of 1 bar to 10 bar. The TiO described in claim 1 2 A method for producing powder.
10. The aforementioned CoO 2 and NH ４ At the stage when Cl is acquired, The aforementioned CoO 2 and NH ４ Cl is obtained from the mixture under temperature conditions of 200°C to 1,000°C. The TiO described in claim 1 2 A method for producing powder.
11. The acquired TiO 2 The process further includes a step in which the powder is subjected to additional heat treatment. The TiO described in claim 1 2 A method for producing powder.
12. The aforementioned CoO 2 During the stage when the powder is subjected to additional heat treatment, The acquired TiO 2 The powder is heat-treated under temperature conditions of 200°C to 1,000°C. The TiO described in claim 11 2 A method for producing powder.
13. NH trapped in residual material after TiN layer formation ３ and TiCl ４ TiO ２ and NH ４ After acquiring Cl, TiO ２ The powder is separated. TiO 2 A method for producing powder.
14. Manufactured by the method described in any one of claims 1 to 13 TiO 2 powder.