Hydrothermal synthesis of cerium-titanium oxide for use in CMP
View Patent ↗The present invention provides a method of synthesizing abrasive particles and methods of using the same in chemical mechanical polishing slurry applications. The nanosized abrasive particles according to the invention are produced by hydrothermal synthesis using an insoluble source of cerium. The crystallites of the particles include cerium ions and titanium ions.
1. A process of making a composite oxide of cerium and titanium comprising: hydrothermally treating, at about 70 to about 500° C., a suspension of deagglomerated composite hydroxide of cerium and titanium in the presence of a Ti +4 source to form a slurry.
2. A process of making a composite oxide of cerium and titanium comprising: hydrothermally treating, at about 70 to about 500° C., a suspension of a deagglomerated, insoluble Ce +4 or Ce +3 source in the presence of a Ti +4 source to form a slurry wherein, prior to hydrothermal treatment, the suspension is deagglomerated to a secondary particle size of less than about 20 microns.
3. A process of making a composite oxide of cerium and titanium comprising: hydrothermally treating, at about 70 to about 500° C., a suspension of deagglomerated Ce(OH) 4 in the presence of a Ti +4 source to form a slurry.
4. A process of making a composite oxide of cerium and titanium comprising:
hydrothermally treating, at about 70 to about 500° C., a suspension of a deagglomerated, insoluble Ce +4 or Ce +3 source in the presence of a Ti +4 source to form a slurry; the process further comprising:
a. cooling the composite oxide slurry to room temperature,
b. decanting excess water from the composite oxide slurry,
c. adjusting the pH of the composite oxide slurry to 4.0±0.5,
d. adding water to the composite oxide slurry,
e. mixing the composite oxide slurry for 1-120 minutes,
f. washing the composite oxide slurry with water,
g. adjusting the composite oxide slurry pH to 4.0±0.5,
h. deagglomerating the composite oxide slurry to afford particles having an average secondary particle size of less than 1 micron, and
i. filtering the particles.
5. The process of claim 2 , wherein the Ce +4 or Ce +3 source is selected from the group consisting of a hydroxide, fluoride, carbonate, phosphate, or oxalate of cerium.
6. The process of claim 5 wherein the Ti +4 source is a soluble titanium compound.
7. The process of claim 5 wherein the Ti +4 source is selected from the group consisting of the halides, perhalides, oxyhalides, nitrates, sulfates, phosphates, carbonates, and acetates of titanium, and organotitanium compounds.
8. The process of claim 5 wherein the Ti +4 source is a titanium alkoxide.
9. The process of claim 5 wherein the Ti +4 source is titanium-acetylacetone or titanium (IV) triethanolaminato isopropoxide.
10. The process of claim 1 , wherein the molar ratio of Ce +4 or Ce +3 to Ti +4 is about 19:1 to about 2:1.
11. The process of claim 1 , wherein the suspension comprises HNO 3 , and wherein the weight ratio of HNO 3 to the Ce +4 or Ce +3 source is about 1/20000 to about 6/100.
12. A process of making a composite oxide of cerium and titanium comprising: hydrothermally treating, at about 70 to about 500° C., a suspension of a deagglomerated, insoluble Ce +4 or Ce +3 source in the presence of a Ti +4 source to form a slurry, wherein the Ce +4 or Ce +3 source is a composite hydroxide of cerium and titanium, wherein the suspension comprises HNO 3 , and wherein the weight ratio of HNO 3 to the Ce +4 or Ce +3 source is about 1/20000 to about 6/100, and wherein, prior to hydrothermal treatment, the suspension is deagglomerated to a secondary particle size of less than about 100 microns.
13. A process of making a composite oxide comprising Ce and Ti for use in CMP, comprising:
a. contacting a cerium-titanium composite hydroxide with aqueous nitric acid to form a suspended precursor, and
b. subjecting the suspended precursor to hydrothermal treatment in a closed vessel at a temperature of 70° C. to about 500° C. for about 0.1 to about 10 hours to form a slurry of composite oxide particles.
14. A process of making a composite oxide comprising Ce and Ti for use in CMP, comprising:
a. contacting a cerium-titanium composite hydroxide with aqueous nitric acid to form a suspended precursor, and
b. subjecting the suspended precursor to hydrothermal treatment in a closed vessel at a temperature of 70° C. to about 500° C. for about 0.1 to about 10 hours to form a slurry of composite oxide particles, wherein:
a. prior to hydrothermal treatment
i. the weight ratio of HNO 3 to the Ce +4 source is about 1/20000 to about 6/100,
ii. the suspended precursor is mixed for about 1 to about 120 minutes at a shear rate of about 1000 to about 10,000 RPM, and
b. after hydrothermal treatment,
i. the suspension is cooled to room temperature,
ii. excess liquid is decanted from the suspension,
iii. the suspension pH is adjusted to 4.0±0.5,
iv. water is added to the suspension,
v. the suspension is mixed for about 1 to about 120 minutes,
vi. the suspension is washed with water until its conductivity is below 200 μS,
vii. the suspension pH is adjusted to 4.0±0.5,
viii. the suspension is deagglomerated to a secondary particle size of less than 1 micron, and
ix. the suspension is filtered.