Increased throughput for large-scale production of low melt organoamine stabilized silver nano-particles
View Patent ↗Process for producing organoamine-stabilized silver nanoparticles with a molar ratio of silver salt to organoamine of about 1:4 to about 1:10 are disclosed. The process includes: forming a solution including an organic solvent and a first amount of organoamine; adding silver salt particles to the solution; adding a second amount of organoamine to the solution; adding a hydrazine to the solution; and reacting the solution to form an organoamine-stabilized silver nanoparticles.
1. A method of producing organoamine-stabilized silver nanoparticles, comprising:
forming a solution comprising an organic solvent and a first amount of organoamine and heating the solution to a first temperature; wherein the first temperature is from about 50° C. to about 80° C.;
adding a silver salt to the solution heated to the first temperature;
adding a second amount of organoamine to the solution heated to the first temperature;
cooling the solution from the first temperature to a second temperature;
adding a hydrazine to the solution to reduce the silver salt forming a reduced silver salt, and reacting the reduced silver salt with the organoamine to form organoamine-stabilized silver nanoparticles while maintaining the solution at the second temperature; and
precipitating the solution after performing the reaction and recovering the organoamine-stabilized silver nanoparticles, by a two-solvent precipitation procedure comprising adding a non-solvent to the solution and then after the non-solvent is added, adding an alcohol to the solution;
wherein the molar ratio of silver salt to total organoamine is from about 1:4 to about 1:10.
2. The method according to claim 1 , wherein the silver salt is selected from the group consisting of silver acetate, silver nitrate, silver oxide, silver acetylacetonate, silver benzoate, silver bromate, silver bromide, silver carbonate, silver chloride, silver citrate, silver fluoride, silver iodate, silver iodide, silver lactate, silver nitrite, silver perchlorate, silver phosphate, silver sulfate, silver sulfide, silver trifluoroacetate and mixtures thereof.
3. The method according to claim 1 , wherein a molar ratio of silver salt to total organoamine is about 1:5.
4. The method according to claim 1 , wherein the organoamine-stabilized silver nanoparticles have a silver content of about 85 percent or more by weight.
5. The method according to claim 1 , wherein the organic solvent is selected from the group consisting of toluene, heptane, hexane, benzene, cyclohexane, pentane, bromobenzene, chlorobenzene, hydrocarbons and mixtures thereof.
6. The method according to claim 1 , wherein the organoamine-stabilized silver nanoparticles have a mean diameter of from about 1 nanometers to about 10 nanometers.
7. The method according to claim 1 , wherein the first temperature is from about 65° C. to about 70° C.
8. The method according to claim 1 , wherein the second temperature is from about 40° C. to about 60° C.
9. The method according to claim 1 , wherein a weight ratio of organic solvent to the first amount of organoamine is from about 1:0.8 to about 1:1.2.
10. The method according to claim 1 , wherein a weight ratio of the first amount of organoamine to the second amount of organoamine is from about 1.7:1.0 to about 1:1.7.
11. The method according to claim 1 , wherein the hydrazine is of the formula:
R 1 R 2 N—NR 3 R 4
wherein R 1 , R 2 , R 3 and R 4 , independently, is hydrogen, an alkyl group of 1 to 30 carbons atoms or an aryl group of 6 to 48 carbons atoms; wherein at least one of the R 1 , R 2 , R 3 and R 4 is not hydrogen.
12. The method according to claim 1 , wherein the hydrazine is first added to a solvent wherein the solvent is selected from the group consisting of an alcohol such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, a hydrocarbon solvent such as pentane, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, toluene, xylene, mesitylene, tetrahydrofuran, or other solvents, such as, chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, cyanobenzene, acetonitrile and mixtures thereof, to produce a hydrazine reducing solution that is added to the solution.
13. The method according to claim 1 , wherein the non-solvent is selected from the group consisting of acetone, methanol, ethanol, propanol, methyl ethyl ketone, acetonitrile, isobutyl alcohol and mixtures thereof.
14. A method of forming conductive features on a substrate, the method comprising:
providing a liquid composition containing the organoamine-stabilized silver nanoparticles produced by the method of claim 1 ,
depositing the liquid composition onto the substrate to form deposited features, and
heating the deposited features on the substrate to a temperature from about 100° C. to about 200° C. to form conductive features on the substrate.
15. The method according to claim 14 , wherein the deposited feature on the substrate is a film and conductivity of the film is 5.5-7.7×10 5 S/cm.
16. The method according to claim 14 , wherein the organoamine-stabilized silver nanoparticles have a narrow particle size distribution such that the difference between the diameter of the largest organoamine-stabilized silver nanoparticle and the diameter of the smallest organoamine-stabilized silver nanoparticle is 10 nanometers.
17. The method according to claim 14 , wherein the organoamine-stabilized silver nanoparticles have a silver content of about 85 percent or more by weight.
18. The method according to claim 14 , wherein the organoamine-stabilized silver nanoparticles have a mean diameter of from about 1 nanometer to about 10 nanometers.
19. The method according to claim 14 , wherein the organoamine-stabilized silver nanoparticles have a mean diameter of from about 2 nanometers to about 8 nanometers.