CN115849430A - Preparation method of monodisperse nano cerium oxide, nano cerium oxide grinding fluid and application thereof - Google Patents
Preparation method of monodisperse nano cerium oxide, nano cerium oxide grinding fluid and application thereof Download PDFInfo
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- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 135
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 238000000227 grinding Methods 0.000 title claims abstract description 40
- 239000012530 fluid Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000005498 polishing Methods 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
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- 239000007788 liquid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 5
- 238000002955 isolation Methods 0.000 claims description 5
- 239000003989 dielectric material Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 42
- 238000003837 high-temperature calcination Methods 0.000 abstract description 13
- 239000005416 organic matter Substances 0.000 abstract description 10
- 238000005054 agglomeration Methods 0.000 abstract description 9
- 230000002776 aggregation Effects 0.000 abstract description 9
- 239000007859 condensation product Substances 0.000 abstract description 6
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- 230000000052 comparative effect Effects 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006061 abrasive grain Substances 0.000 description 2
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- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
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- 230000002457 bidirectional effect Effects 0.000 description 1
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- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a preparation method of monodisperse nano cerium oxide, nano cerium oxide grinding fluid and application thereof, wherein cerium carbonate is used as a preparation raw material, decomposable organic matter containing carboxyl and amino is added into the cerium carbonate dispersion fluid before high-temperature calcination, in the high-temperature calcination process, the organic matter containing carboxyl and amino reacts under the high-temperature action to generate a condensation product similar to small chambers, further, the cerium carbonate is decomposed under the high-temperature action, the generated cerium oxide crystal nucleus grows regularly under the separation action of the small chambers, finally, the cerium oxide crystal which has uniform particle shape, keeps a monodisperse state and has no obvious hard agglomeration is obtained, and the condensation product is finally completely volatilized and removed under the high-temperature action. The invention realizes the aim of obtaining monodisperse nano cerium oxide in the high-temperature calcination process by optimizing and improving the preparation method of cerium oxide, and the improved preparation method is simple to operate and convenient for commercial popularization.
Description
Technical Field
The invention relates to the technical field of rare earth oxide material preparation, and particularly relates to a preparation method of monodisperse nano cerium oxide, nano cerium oxide grinding fluid and application thereof.
Background
Cerium oxide is widely used as abrasive grains in chemical mechanical polishing liquids for integrated circuits because of its unique chemical mechanical synergistic effect in planarization of silicon oxide. Common application scenarios are chemical mechanical planarization of shallow trench isolation techniques and interlayer dielectric techniques. The chemical mechanical polishing slurry used in the integrated circuit manufacturing process is mainly required to have a stable material removal rate and low surface defects. This requires that the cerium oxide particles as abrasive grains have a uniform size and good dispersion characteristics. This makes optimizing the preparation method of cerium oxide and improving the chemical mechanical planarization effect become the hot point of research in recent years.
For the preparation of nano cerium oxide and the research of the chemical mechanical planarization performance, the common preparation methods include a precipitation method, a molten salt method, a hydrothermal method and the like. The preparation method of cerium oxide in the commercial grinding fluid is still a precipitation and calcination method, the prepared cerium oxide is usually in an agglomerated and hardened state, and the cerium oxide particles after high-temperature sintering are dispersed by mechanical crushing before use. This not only increases the energy consumption, but also makes the preparation process of the grinding fluid complicated and lengthy. Meanwhile, the nano cerium oxide grinding fluid obtained by mechanical grinding has poor particle size distribution, so that the dispersion stability of cerium oxide in the grinding fluid is poor.
Therefore, the synchronous realization of the preparation of the monodisperse nano cerium oxide in the high-temperature calcination process is a technical difficulty which needs to be overcome by technical personnel.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of monodisperse nano cerium oxide, nano cerium oxide grinding fluid and application thereof.
The specific invention content is as follows:
in a first aspect, the present invention provides a method for preparing monodisperse nano cerium oxide, the method comprising:
s1, dispersing cerium carbonate in constant-temperature water at 50-140 ℃ to obtain cerium carbonate dispersion liquid;
s2, adding decomposable organic matters containing carboxyl and amino into the cerium carbonate dispersion liquid to obtain a mixed solution;
and S3, carrying out high-temperature roasting and annealing treatment on the mixed solution to obtain the monodisperse nano cerium oxide.
Optionally, in the step 1, the mass ratio of the cerium carbonate to the constant-temperature water is 1:2-20.
Optionally, in the step 1, the mass ratio of the cerium carbonate to the constant-temperature water is 1:5-15.
Optionally, in step 2, the organic matter is at least one of urea, amino acid, carbamyl urea and melamine;
the mass ratio of the organic matters to the constant-temperature water is 1:2-20.
Optionally, in step 2, the organic matter is urea;
the mass ratio of the organic matters to the constant-temperature water is 1:5-15.
Optionally, in the step 3, the high-temperature roasting temperature is 600-1000 ℃, and the high-temperature roasting time is 4-10 h;
the annealing temperature is 400-500 ℃, and the annealing time is 2-4 h.
In a second aspect, the present invention provides a nano cerium oxide slurry, wherein the nano cerium oxide slurry is composed of the nano cerium oxide prepared by the preparation method of the first aspect and deionized water;
the preparation method of the nano cerium oxide grinding fluid comprises the following steps: dispersing the monodisperse nano cerium oxide in deionized water by stirring and ultrasonic dispersion to obtain nano cerium oxide grinding fluid;
the ultrasonic dispersion time is 4-10 h.
Optionally, the nano cerium oxide grinding fluid further comprises an anionic surfactant and/or a pH regulator;
the preparation method of the nano cerium oxide grinding fluid comprises the following steps: dispersing the monodisperse nano cerium oxide in deionized water containing an anionic surfactant and a pH regulator by stirring and ultrasonic dispersion to obtain nano cerium oxide grinding fluid;
the time of ultrasonic dispersion is 4-10 h.
Optionally, the anionic surfactant is polyacrylic acid and salts thereof, and the weight average molecular weight of the anionic surfactant is 1000-10000;
the mass ratio of the anionic surfactant to the monodisperse nano cerium oxide is 1:10-100 parts of;
the pH regulator is nitric acid, sulfuric acid, hydrochloric acid or sodium hydroxide;
the pH value of the nano cerium oxide grinding fluid is 4-10.
In a third aspect, the present invention provides an application of the nano cerium oxide polishing solution according to the second aspect in chemical mechanical planarization of integrated circuits, wherein the nano cerium oxide polishing solution is used for shallow trench isolation and chemical mechanical planarization of interlayer dielectrics.
Compared with the prior art, the invention has the following advantages:
the invention provides a preparation method of monodisperse nano cerium oxide, which takes cerium carbonate as a preparation raw material, before high-temperature calcination, decomposable organic matter containing carboxyl and amino is added into cerium carbonate dispersion liquid, in the high-temperature calcination process, the organic matter containing carboxyl and amino reacts under the high-temperature action in advance to generate a condensation product similar to small chambers, further, the cerium carbonate decomposes under the high-temperature action, the generated cerium oxide crystal nucleus grows regularly under the separation action of the small chambers, finally, the cerium oxide crystal which has uniform particle shape, keeps a monodisperse state and has no obvious hard agglomeration is obtained, and the condensation product is finally volatilized and removed completely under the high-temperature action.
The invention realizes the aim of obtaining monodisperse nano cerium oxide in the high-temperature calcination process by optimizing and improving the preparation method of cerium oxide, and the improved preparation method is simple to operate and convenient for commercial popularization. The obtained nano cerium oxide particles have uniform particle size, no obvious hard agglomeration and clear particle boundaries under an electron microscope image. When the monodisperse nano cerium oxide grinding fluid provided by the embodiment of the invention is used for preparing the nano cerium oxide grinding fluid, the nano cerium oxide grinding fluid can be directly dispersed in a liquid phase only by ultrasonic mechanical stirring, so that the hardened and agglomerated cerium oxide particles are not dispersed by a mechanical crushing method before the existing nano cerium oxide grinding fluid is prepared. Effectively reduces energy consumption, shortens the preparation process of the polishing solution and improves the dispersion stability of the cerium oxide in the nano cerium oxide grinding solution. The average secondary particle size of the cerium oxide particles can be between 1 and 3 times the average primary particle size by simple mechanical stirring.
The invention also provides a nano cerium oxide grinding fluid which is applied to the chemical mechanical planarization process of integrated circuits, can be particularly applied to the chemical mechanical planarization of shallow trench isolation and interlayer dielectrics, and can obtain higher silicon oxide removal rate and keep lower defects.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of a method for preparing monodisperse nano cerium oxide according to an embodiment of the present invention;
fig. 2 shows an SEM image and a primary particle size distribution diagram of monodisperse nano cerium oxide particles provided by an embodiment of the present invention;
FIG. 3 shows SEM images of monodisperse nano-cerium oxide particles provided in examples 2-5 of the present invention;
fig. 4 shows an SEM image of nano cerium oxide particles provided in comparative example 1 of the present invention;
FIG. 5 shows an SEM image of nano-cerium oxide particles provided in comparative example 2 of the present invention;
FIG. 6 shows an SEM image of monodisperse nano-cerium oxide particles provided by an embodiment of the present invention after dispersion;
FIG. 7 shows X-ray diffraction patterns of nano-cerium oxide particles prepared in inventive example 1, comparative example 1 and comparative example 2;
FIG. 8 is a graph showing the comparison of the material removal rates of silicon dioxide and silicon nitride by adjusting the pH of the nano cerium oxide polishing solution in example 1.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The specific experimental procedures or conditions are not indicated in the examples and can be performed according to the procedures or conditions of the conventional experimental procedures described in the prior art in this field. The reagents and other instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
The invention considers that the cerium oxide prepared by the prior art is usually hardened or in an agglomerated state rather than a dispersed state, and when the cerium oxide is used for preparing the nano cerium oxide grinding fluid, the cerium oxide cannot be directly dispersed in a liquid phase, but mechanical crushing is firstly carried out, so that cerium oxide particles after high-temperature sintering are dispersed. The process not only has high energy consumption, but also has poor particle size distribution and poor dispersion stability of the obtained nano cerium oxide grinding fluid. In view of the above, the present inventors have searched for a conventional method for preparing cerium oxide, and have made an effort to obtain monodisperse nano cerium oxide by improving a process flow of preparing cerium oxide by a calcination method, and calcining cerium carbonate as a raw material at a high temperature. The specific implementation content is as follows:
the first objective of the present invention is to provide a method for preparing monodisperse nano cerium oxide, and fig. 1 shows a flow chart of a method for preparing monodisperse nano cerium oxide provided by an embodiment of the present invention, as shown in fig. 1, the method includes:
s1, dispersing cerium carbonate in constant-temperature water at 50-140 ℃ to obtain cerium carbonate dispersion liquid;
s2, adding decomposable organic matters containing carboxyl and amino into the cerium carbonate dispersion liquid to obtain a mixed solution;
and S3, carrying out high-temperature roasting and annealing treatment on the mixed solution to obtain the monodisperse nano cerium oxide.
In the specific implementation, before the cerium carbonate serving as a reaction raw material is calcined at a high temperature, decomposable organic matters containing carboxyl and amino are added into a cerium carbonate dispersion liquid, in the high-temperature calcination process, the organic matters containing carboxyl and amino react under the action of the high temperature to generate a condensation product similar to small chambers, further, the cerium carbonate is decomposed under the action of the high temperature, generated cerium oxide nuclei grow regularly under the separation action of the small chambers, and finally, the cerium oxide crystals which are uniform in particle shape, maintain a monodispersed state and have no obvious hard agglomeration are obtained, and the condensation product is finally completely volatilized and removed under the action of the high temperature.
Further, care should be taken to control the temperature of the cerium carbonate dispersion to be maintained at 50 ℃ to 140 ℃, and at this temperature, the cerium carbonate can maintain a bidirectional reaction state of dissolution and precipitation, which is favorable for the subsequent decomposable carboxyl and amino containing organic matter to be fully and uniformly mixed in the cerium carbonate dispersion, and the added carboxyl and amino containing organic matter is not decomposed.
The invention realizes the aim of obtaining monodisperse nano cerium oxide in the high-temperature calcination process by optimizing and improving the preparation method of cerium oxide, and the improved preparation method is simple to operate and convenient for commercial popularization. The obtained nano cerium oxide particles have uniform particle size, no obvious hard agglomeration and clear particle boundaries under an electron microscope image. Can be directly dispersed in the liquid phase only by ultrasonic mechanical stirring. The average secondary particle size can be between 1 and 3 times the average primary particle size by simple mechanical agitation.
In specific implementation, the steps S1 and S2 can be performed in a constant-temperature oil bath, stirring is required to add the decomposable organic matter containing carboxyl and amino into the cerium carbonate dispersion, and the stirring time can be controlled within 60min to 360min, preferably within 120min to 240min.
In some embodiments, in step 1, the mass ratio of cerium carbonate to thermostatic water needs to be controlled to be 1:2-20; the mass ratio of the cerium carbonate to the constant-temperature water is controlled to be 1:5-15.
In some embodiments, in step 2, the organic substance may be selected from at least one of urea, amino acid, carbamyl urea, and melamine; the mass ratio of the organic matters to the constant-temperature water is 1:2-20.
Among them, urea is a preferred organic compound; the mass ratio of the organic matter to the constant-temperature water is preferably 1:5-15.
In some embodiments, in step 3, the temperature of the high-temperature roasting needs to be controlled to be 600-1000 ℃, and the time of the high-temperature roasting needs to be controlled to be 4-10 h; the annealing temperature is controlled to be 400-500 ℃, and the annealing time is controlled to be 2-4 h.
The second objective of the present invention is to provide a nano cerium oxide polishing solution, which comprises the nano cerium oxide prepared by the preparation method of the first aspect and deionized water.
The nano cerium oxide particles prepared by the method have uniform particle size, do not have obvious hard agglomeration, have clear particle boundaries under an electron microscope image, and can be directly dispersed in a liquid phase only by means of ultrasonic mechanical stirring. Therefore, when the method is used for preparing the nano cerium oxide grinding fluid, the monodisperse nano cerium oxide is directly dispersed in deionized water through stirring and ultrasonic dispersion, and the nano cerium oxide grinding fluid can be obtained; the time of ultrasonic dispersion is controlled to be 4-10 h. The method avoids the need of dispersing the hardened and agglomerated cerium oxide particles by a mechanical crushing method before the preparation of the existing nano cerium oxide grinding fluid. Effectively reduces the energy consumption, shortens the preparation process of the polishing solution and improves the dispersion stability of the cerium oxide in the nano cerium oxide grinding solution.
In some embodiments, the nano cerium oxide abrasive solution may further contain an anionic surfactant and/or a pH adjusting agent to further accommodate different polishing objects. The anionic surfactant can be polyacrylic acid and its salt, and has weight average molecular weight of 1000-10000; the mass ratio of the anionic surfactant to the monodisperse nano cerium oxide is 1:10-100 parts of; the pH regulator is nitric acid, sulfuric acid, hydrochloric acid or sodium hydroxide; the pH value of the nano cerium oxide grinding liquid is 4-10.
The third objective of the present invention is to provide an application of the nano cerium oxide polishing slurry according to the second aspect in chemical mechanical planarization of integrated circuits, in particular, for chemical mechanical planarization of shallow trench isolation and interlayer dielectrics.
In order to make the present application more clearly understood by those skilled in the art, the preparation method of the monodisperse nano cerium oxide, the nano cerium oxide polishing solution and the application thereof described in the present application will now be described in detail by the following examples.
Example 1:
cerium carbonate and water were mixed at a mass ratio of 1. Urea was added to a mixture of cerium carbonate and water, which was heated and stirred at a constant temperature, in the same mass as that of cerium carbonate. The mixture was then stirred for 120min with continued constant temperature heating. Subsequently, the mixture was washed with water 3 times, and then placed in a muffle furnace and calcined at a high temperature of 900 ℃ for 10 hours. After high temperature calcination, annealing was carried out at 400 ℃ for 2h.
And dispersing the annealed cerium oxide in water, ultrasonically stirring the mixture for 6 hours, and then adjusting the pH value to obtain cerium oxide grinding slurry.
Fig. 2 shows an SEM image and a primary particle size distribution diagram of the monodisperse nano cerium oxide particles provided in the embodiment of the present invention, and as shown in fig. 2, the monodisperse nano cerium oxide particles have clear particle boundaries, uniform particle sizes, and no obvious hard agglomeration under the electron microscope image.
Examples 2 to 5:
cerium carbonate and water were mixed at a mass ratio of 1. Urea was added to a mixture of cerium carbonate and water, which was heated and stirred at a constant temperature, in the same mass as that of cerium carbonate. The mixture was then stirred for 120min with continued constant temperature heating. Subsequently, the mixture was washed with water 3 times and then placed in a muffle furnace. The calcination temperatures of examples 2 to 5 were 600 ℃,700 ℃,800 ℃ and 1000 ℃ in this order. The high-temperature roasting time is 10 hours. After high temperature calcination, annealing at 400 ℃ for 2h.
Fig. 3 shows SEM images of monodisperse nano-cerium oxide particles provided in examples 2-5 of the present invention.
Comparative example 1:
cerium carbonate and water were mixed at a mass ratio of 1. Oxalic acid was added to a mixture of cerium carbonate and water, which was heated and stirred at a constant temperature, in the same mass as that of cerium carbonate. The mixture was then stirred for 120min with continued constant temperature heating. Subsequently, the mixture was washed with water 3 times, and then placed in a muffle furnace and calcined at a high temperature of 900 ℃ for 10 hours. After high temperature calcination, annealing at 400 ℃ for 2h.
And dispersing the annealed cerium oxide in water, and ultrasonically stirring the mixture for 6 hours to obtain cerium oxide grinding slurry.
Fig. 4 shows an SEM image of the nano cerium oxide particles provided in comparative example 1 of the present invention, and as shown in fig. 4, the nano cerium oxide particles provided in comparative example 1 have a significant agglomeration phenomenon.
Comparative example 2:
mixing cerium carbonate and water according to a mass ratio of 1. Subsequently, the mixture was washed with water 3 times, and then placed in a muffle furnace and calcined at a high temperature of 900 ℃ for 10 hours. After high temperature calcination, annealing at 400 ℃ for 2h.
And dispersing the annealed cerium oxide in water, and ultrasonically stirring the mixture for 6 hours to obtain cerium oxide grinding slurry.
TABLE 1 laser particle sizer test results for cerium oxide grinding fluids
Fig. 5 shows an SEM image of the nano cerium oxide particles provided in comparative example 2 of the present invention, and as shown in fig. 5, the nano cerium oxide particles provided in comparative example 2 also have an agglomeration phenomenon.
FIG. 6 shows an SEM image of monodisperse nano-cerium oxide particles provided by an embodiment of the present invention after dispersion; table 1 shows the laser particle size analyzer test results of the cerium oxide polishing slurry provided in the embodiments of the present invention, and as shown in fig. 6 and table 1, the monodisperse nano cerium oxide particles provided in the embodiments of the present invention can achieve an average secondary particle size of the monodisperse nano cerium oxide particles between 1 and 3 times of the average primary particle size through simple mechanical stirring.
Fig. 7 is an X-ray diffraction pattern of nano cerium oxide particles prepared in example 1 of the present invention, comparative example 1 and comparative example 2.
FIG. 8 is a graph showing the comparison of the polishing rates of the nano cerium oxide abrasive solution for silicon dioxide and silicon nitride after adjusting different pH values in example 1 of the present invention.
Table 2 results of laser particle size analyzer test and polishing rate results for silicon dioxide and silicon nitride after adjusting different PH for the nano cerium oxide polishing solution provided in example 1 of the present invention
The preparation method of the monodisperse nano cerium oxide, the nano cerium oxide grinding fluid and the application thereof provided by the invention are described in detail, the principle and the embodiment of the invention are explained by applying specific examples, and the description of the examples is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (10)
1. A method for preparing monodisperse nano cerium oxide, which is characterized by comprising the following steps:
s1, dispersing cerium carbonate in constant-temperature water at 50-140 ℃ to obtain cerium carbonate dispersion liquid;
s2, adding decomposable organic matters containing carboxyl and amino into the cerium carbonate dispersion liquid to obtain a mixed solution;
and S3, carrying out high-temperature roasting and annealing treatment on the mixed solution to obtain the monodisperse nano cerium oxide.
2. The preparation method according to claim 1, wherein in step 1, the mass ratio of the cerium carbonate to the constant-temperature water is 1:2-20.
3. The preparation method according to claim 1, wherein in step 1, the mass ratio of the cerium carbonate to the constant-temperature water is 1:5-15.
4. The method according to claim 1, wherein in step 2, the organic substance is at least one of urea, an amino acid, carbamyl urea, and melamine;
the mass ratio of the organic matters to the constant-temperature water is 1:2-20.
5. The method according to claim 1, wherein in step 2, the organic substance is urea;
the mass ratio of the organic matters to the constant-temperature water is 1:5-15.
6. The preparation method according to claim 1, wherein in the step 3, the high-temperature roasting temperature is 600-1000 ℃, and the high-temperature roasting time is 4-10 h;
the annealing temperature is 400-500 ℃, and the annealing time is 2-4 h.
7. A nano cerium oxide grinding fluid is characterized by consisting of monodisperse nano cerium oxide prepared by the preparation method of any one of claims 1 to 6 and deionized water;
the preparation method of the nano cerium oxide grinding fluid comprises the following steps: dispersing the monodisperse nano cerium oxide in deionized water by stirring and ultrasonic dispersion to obtain nano cerium oxide grinding fluid;
the time of ultrasonic dispersion is 4-10 h.
8. The nano cerium oxide polishing solution according to claim 7, further comprising an anionic surfactant and/or a pH regulator;
the preparation method of the nano cerium oxide grinding fluid comprises the following steps: dispersing the monodisperse nano cerium oxide in deionized water containing an anionic surfactant and a pH regulator by stirring and ultrasonic dispersion to obtain nano cerium oxide grinding fluid;
the time of ultrasonic dispersion is 4-10 h.
9. The nano cerium oxide polishing solution according to claim 8, wherein the anionic surfactant is polyacrylic acid and salts thereof, and the weight average molecular weight of the anionic surfactant is 1000 to 10000;
the mass ratio of the anionic surfactant to the monodisperse nano cerium oxide is 1:10-100 parts of;
the pH regulator is nitric acid, sulfuric acid, hydrochloric acid or sodium hydroxide;
the pH value of the nano cerium oxide grinding fluid is 4-10.
10. The use of the nano cerium oxide abrasive fluid of claim 7 in the chemical mechanical planarization of integrated circuits, wherein the nano cerium oxide abrasive fluid is used for shallow trench isolation and the chemical mechanical planarization of interlayer dielectrics.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1699282A (en) * | 2005-06-09 | 2005-11-23 | 江苏工业学院 | Preparation of monodisperse spherical cerium oxide and its application in high precision polishing |
| KR20060134383A (en) * | 2005-06-22 | 2006-12-28 | 주식회사 엘지화학 | Method for preparing cerium oxide nano powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1699282A (en) * | 2005-06-09 | 2005-11-23 | 江苏工业学院 | Preparation of monodisperse spherical cerium oxide and its application in high precision polishing |
| KR20060134383A (en) * | 2005-06-22 | 2006-12-28 | 주식회사 엘지화학 | Method for preparing cerium oxide nano powder |
Non-Patent Citations (1)
| Title |
|---|
| 邢振平等: "《轴承零件加工质量缺陷分析及防控措施》", vol. 1, 31 May 2020, 武汉理工大学出版社, pages: 135 * |
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