KR100417529B1 - Synthesis of nano size Cerium Oxide by Glycothermal Processing - Google Patents

Abstract

The present invention relates to the production of cerium oxide particles used as a catalyst or an abrasive, the method of producing nano-sized ceria powder under high temperature and high pressure using an organic solvent in the production of cerium oxide particles, the particle diameter is less than 100 nanometers (nm) and size distribution Relates to a method for producing uniform fine cerium oxide particles.

Description

Synthesis method of nano size ceria powder by glyco thermal method {Synthesis of nano size Cerium Oxide by Glycothermal Processing}

Particle size and shape of the ceramic powder is one of the important factors to determine the physical properties of the ceramic. Therefore, many researchers are doing research to control the size and shape of the oxide particles.

In the present invention, the powder synthesis process using the organic solvent is the same as the hydrothermal synthesis method and the organic solvent is used as the main reaction solvent. In this study, we tried to control the particle size by inducing dissolution and re-precipitation in glycol-based solvents using amorphous hydroxide by precipitation. Since glycol, which is a solvent used in the experiment, is a solvent having a slight viscosity at room temperature, glycol, distilled water and other additives are mixed with a magnetic stirrer according to each experiment composition, and then the ceria precursor powder is put in ultrasonic wave for uniform mixing and dispersion. The reaction was attempted in the reactor by mixing for about 5 minutes using a disperser.

Considering the problems of conventional cerium oxide particle production, it is possible to economically mass-produce mass, develop particle manufacturing method that has small particle size (less than 100nm), uniform size distribution and spherical shape, and has large specific surface area and high temperature. It is an object of the present invention to develop a method for producing fine cerium oxide particles which is stable even in the form of a catalyst or a catalyst support and excellent as a raw material for a slurry for semiconductor polishing. CMP (Chemical Mechanical Polishing) is a mechanical removal processing technology that combines the chemical action of nano-ceramic particles and the physical external force applied to the pad. It is used in the ultra-high density semiconductor manufacturing process and used according to the characteristics of the polishing surface. Dielectric can be classified into CMP, STI (Shallow Trench Isolation) CMP, and Metal CMP. Factors affecting the CMP process include slurry, material and structure of the pad, process equipment, material to be polished, wafer pattern shape and density, and the like. In particular, the components of the slurry and the physical properties of the pad should be adjusted according to the process equipment, polishing conditions, and materials to be polished. Silica (SiO ₂ ) as the nanoparticles of the slurry for ILD CMP, Ceria (CeO ₂ ) as the slurry for STI CMP, and silica (SiO ₂ ) and alumina (Al ₂ O ₃ ) as the slurry for the metal CMP are widely used. In particular, the STI CMP slurry has CeO ₂ particles with high selectivity in device design with a minimum line width of 0.17㎛ or less.

Ceria particles used at present are being synthesized by an emulsion method having a high production cost, and thus a cheaper synthesis method is being sought. In addition, the present invention seeks to synthesize a powder having a high crystallinity, high affinity for organic compounds, and excellent magnetic properties.

The technical field of the present invention belongs to the manufacturing and utilization of fine metal particles, the conventional method for producing the fine metal particles are largely a technique for producing nanoparticles in the gas phase, such as aerosol method and evaporation / condensation method and a solution containing a reducing agent in the metal ion solution The coprecipitation method for preparing nanoparticles by mixing the nanoparticles has been widely developed. In the case of the coprecipitation method, the metal ions in the solution and the hydroxyl group of the reducing agent are combined to obtain a precipitate in the form of hydroxide. The precipitate is dried and calcined to produce nano ceramic particles.

Particle size and shape of the ceramic powder is one of the important factors to determine the physical properties of the ceramic. Therefore, many researchers are doing research to control the size and shape of the oxide particles.

The present invention relates to a method of controlling the shape and size of cerium oxide powder at an appropriate temperature and pressure conditions using an organic solvent, unlike the conventional hydrothermal synthesis method.

Recently, there has been a great increase in research on ceramic powder synthesis and its commercial application. In general, powder manufacturing using a solid phase is impossible to produce fine particles of 1 ㎛ or less, there is a disadvantage that the initial raw material and composition can be different. In addition, liquid powder synthesis methods such as coprecipitation method, hydrothermal synthesis method and sol-gel method have been actively studied to solve this problem because it is not easy to control the shape of the powder. Among them, a relatively easy method of composition, particle size, and shape control has been studied as a hydrothermal synthesis method using an appropriate temperature and pressure, and some commercial applications have been made.

Ceria particles used at present are being synthesized by an emulsion method having a high production cost, and thus a cheaper synthesis method is being sought. In addition, the present invention seeks to synthesize a powder having a high crystallinity, high affinity for organic compounds, and excellent magnetic properties.

Currently, the study by hydrothermal synthesis method is interested in the synthesis of powder using a metal organic compound instead of salt or hydroxide as a starting material or using an organic solvent rather than an aqueous solution. For example, RS Sapiesko & E. Matijevi C reacts ferric salt with various chelating agents such as TEA and EDTA in a basic atmosphere to chelate them, and then oxidizes them with an oxidizing agent or reducing agent to control the degree of oxidation. By decomposing, α-Fe ₂ O ₃ and Fe ₃ O ₄ could be obtained. In addition, a new powder synthesis method for synthesizing uniform powders at lower temperatures and pressures than hydrothermal synthesis conditions by forming complexes or derivatives between metal ions and organic solvents using mainly organic solvents without the use of separate chelating agents or metal chelates Research on this has been reported.

Based on the results of the previous studies, instead of an aqueous solution, glycol, a dihydric alcohol, was used to stably grow the crystalline particles through chelate reaction and to reduce the crystallization temperature to prepare a powder having a nano size crystal. On the other hand, many studies on hydrothermal synthesis for synthesizing ceria have been reported, but there are no studies on synthesizing cerium oxide using glycol as a solvent.

Therefore, in this study, nanoscale ceria particles were prepared by glycothermal reaction using glycol as a solvent. In this study, ethylene glycol was used as a solvent and various additives were added to investigate the effects on the size and shape of the powder and to establish appropriate conditions.

1 is a manufacturing process diagram of the present invention

2 is a TEM photograph of cerium oxide particles prepared according to the present invention.

XRD graph of cerium oxide particles

4 is a TEM photograph of cerium oxide particles prepared according to the present invention.

5 is a TEM photograph of cerium oxide particles prepared according to the present invention.

6 is a TEM photograph of cerium oxide particles prepared according to the present invention.

In the method for preparing nano-sized ceria powder by the glyco thermal method of the present invention, using a cerium precursor as a starting material, and using Glycol as a solvent, the temperature is 150-300 ° C., the pressure is 3-30 kgf / cm ² , and the reaction time is 1-48. Under the condition of, it is characterized in that the ceria powder is synthesized by adding a form and particle size regulator. At this time, the cerium precursor is Ce (NO ₃ ) ₃ · 6H ₂ O, Ce ₂ (C ₂ O ₄ ) ₃ · χH ₂ O , Ce ₂ (SO ₄ ) ₃ · χH ₂ O, and the concentration may be in the range 0.1-2 mol / l. The glycol solvent used at this time is selected from ethylene glycol, propylene glycol, 1-4 butanediol It may be in the form of one or two or more complex solvents, and the particle size and shape control agent used may be selected from water, itaconic acid, HNO ₃ to control the size and shape of the particles. The procedure is the same and organic solvent is used as the main reaction solvent. In this study, we tried to control the particle size by inducing dissolution and re-precipitation in glycol-based solvents using amorphous hydroxide by precipitation. Since glycol, which is a solvent used in the experiment, is a solvent having a slight viscosity at room temperature, glycol, distilled water, and other additives may be added to each experimental composition because precursors in the form of hydrates are not dispersed well in the glycol solution by mechanical stirring. The mixture was mixed with a magnetic stirrer, and then ceria precursor powder was added and mixed for about 5 minutes using an ultrasonic disperser for uniform mixing and dispersion. The powder produced by this reaction was divided into 50 ml centrifuge tubes, centrifuged at 2000-9000 rpm, and then crystal phases and shapes were examined.

As shown in FIG. 1, 5 g of Ce (OH) _{2 was} dissolved in etyelene glycol 220 ml, and then 30 ml of water was added to observe the shape of the powder obtained by reaction at 230 ° C. for 6 hours in a reactor. A particle of 30 nm size was obtained.

As for the crystal phase of the obtained powder, it was confirmed by X-ray diffraction analysis that CeO ₂ was formed as shown in FIG.

Example 2

5 g of Ce (OH) ₂ was dissolved in 210 ml of etyelene glycol, and 40 ml of water was added to observe the shape of the powder obtained by reacting at 230 ° C. for 6 hours in a reactor. Particles were obtained.

Example 3

5 g of Ce (OH) 2 was dissolved in 100 ml of etyelene glycol, and then 150 ml of water was added to observe the shape of the powder obtained by reaction at 200 ° C. for 6 hours in a reactor. Powder was obtained.

Example 4

5 g of Ce (OH) 2 was dissolved in 50 ml of etyelene glycol and 200 ml of water was added to observe the shape of the powder obtained by reaction at 200 ° C. for 6 hours in a reactor. Powder was obtained.

By controlling the size and shape of the ceria powder by the Glycothermal method, a method that can be applied to various other oxide powder compositions is presented.

As an effect of the invention

-Easy to mass production of various fine cerium oxide particles with economical and simple manufacturing process

-The particle size is fine (100 nm or less) and the size distribution is uniform, so the particle performance is excellent.

Even after firing at high and low temperatures, the specific surface is large, making it well suited for catalyst applications such as catalysts or catalyst supports.

-Suppresses the polygonal Molphology of fine cerium oxide particles to create spherical particles to solve the scratch problem in the existing semiconductor CMP process

-The particle size is small and the dispersion stability is large, so it can be used very well for the manufacture of slurry for STI CMP.

Claims (6)

It is characterized by synthesizing ceria powder by using a cerium precursor as a starting material and adding Glycol as a solvent under the conditions of temperature 150-300 ° C., pressure 3-30 kgf / cm ² , and reaction time 1-48. The manufacturing method of the nano-sized ceria powder by the glyco-thermal method which makes it. The cerium precursor of claim 1, wherein the cerium precursor is one of Ce (NO ₃ ) ₃ · 6H ₂ O, Ce ₂ (C ₂ O ₄ ) ₃ · χH ₂ O, Ce ₂ (SO ₄ ) ₃ · χH ₂ O, and the concentration is The method for producing a nano-sized ceria powder by the glyco thermal method, characterized in that 0.1 to 2 mol / l range. The method of claim 1, wherein the solvent used is one or two or more complex solvents selected from ethylene glycol, propylene glycol, and 1-4 butanediol. delete The method for producing a nano-sized ceria powder by glyco thermal method according to claim 1, wherein the particle size and shape adjusting agent used is one or two or more selected from water, itaconic acid and HNO ₃ . delete