Methods for forming lead zirconate titanate nanoparticles
View Patent ↗Methods for forming lead zirconate titanate (PZT) nanoparticles are provided. The PZT nanoparticles are formed from a precursor solution, comprising a source of lead, a source of titanium, a source of zirconium, and a mineralizer, that undergoes a hydro thermal process. The size and morphology of the PZT nanoparticles are controlled, in part, by the heating schedule used during the hydro thermal process.
1. A method of forming a plurality of piezoelectric perovskite lead zirconium titanate (PZT) nanoparticles, the method comprising the steps of:
(a) providing a precursor solution comprising a mineraliser, titanium isopropoxide, zirconium n-propoxide, lead acetate trihydrate, acetylacetone, and water, wherein the lead acetate trihydrate, zirconium n-propoxide, and titanium isopropoxide are present in the precursor in a weight ratio of from about 1 to about 2 parts lead acetate trihydrate, from about 0.5 to about 1 parts zirconium n-propoxide, and from about 0.8 to about 1.6 parts titanium isopropoxide, and wherein the precursor solution comprises from about 10% to about 90%, by weight, of excess lead; and
(b) heating the precursor solution to produce PZT nanoparticles, wherein heating the precursor solution comprises a first heating schedule that includes at least the sequential steps of:
(i) heating the precursor solution at a first rate to a first temperature, wherein said first rate is greater than about 1° C./min, and wherein said first temperature is between about 120° C. and about 350° C.;
(ii) holding for a first hold time at the first temperature, wherein said first hold time is between about 5 to about 300 minutes; and
(iii) cooling at a second rate to provide a nanoparticle PZT solution comprising a suspended plurality of perovskite PZT nanoparticles having a smallest dimension of between about 20 nm and about 1000 nm, wherein said second rate is greater than about 1° C./min.
2. The method of claim 1 , wherein the first rate is sufficiently fast that the PZT nanoparticles do not nucleate in the precursor solution during heating.
3. The method of claim 1 , wherein during the first hold time the PZT nanoparticles nucleate to provide a nanoparticle solution comprising a suspended plurality of PZT nanoparticles.
4. The method of claim 1 , wherein the second rate is sufficiently fast that the nanoparticle PZT solution becomes supersaturated.
5. The method of claim 1 , wherein the mineraliser is selected from the group comprising KOH, NaOH, LiOH, NH4OH, and combinations thereof.
6. The method of claim 1 , wherein the mineraliser has a concentration of between about 0.2 M and about 15 M.
7. The method of claim 1 , wherein the first heating schedule is performed in a pressure-controlled atmosphere having a pressure of between about 1 atm and about 20 atm.
8. The method of claim 1 , wherein the plurality of perovskite PZT nanoparticles have the formula PbxZiyTizO3, wherein x is between 0.8 and 2, wherein y is between 0.4 and 0.6, and wherein y plus z equals 1.
9. The method of claim 1 , wherein the lead acetate trihydrate, zirconium n-propoxide, and titanium isopropoxide are present in the precursor in a weight ratio of greater than 1 to about 2 parts lead acetate trihydrate, from about 0.5 to about 1 parts zirconium n-propoxide, and from about 0.8 to about 1.6 parts titanium isopropoxide.
10. The method of claim 1 , wherein the first rate is greater than about 10° C./min.
11. The method of claim 1 , wherein the second rate is greater than about 10° C./min.
12. The method of claim 1 , wherein the precursor solution includes about 40% to about 60%, by weight, of excess lead.
13. The method of claim 1 , wherein the precursor solution includes about 50% to about 90%, by weight, of excess lead.
14. The method of claim 1 , wherein the step of heating the precursor solution at a first rate comprises placing the precursor solution into a furnace heated to the first temperature.
15. A method of forming a plurality of piezoelectric perovskite lead zirconium titanate (PZT) nanoparticles, the method comprising the steps of:
(a) providing a precursor solution comprising a mineraliser, titanium isopropoxide, zirconium n-propoxide, lead acetate trihydrate, acetylacetone, and water, wherein the lead acetate trihydrate, zirconium n-propoxide, and titanium isopropoxide are present in the precursor in a weight ratio of from about 1 to about 2 parts lead acetate trihydrate, from about 0.5 to about 1 parts zirconium n-propoxide, and from about 0.8 to about 1.6 parts titanium isopropoxide; and
(b) heating the precursor solution to produce PZT nanoparticles, wherein heating the precursor solution comprises a first heating schedule that includes at least the sequential steps of:
(i) heating the precursor solution at a first rate to a first temperature by placing the precursor solution into a furnace heated to the first temperature, wherein said first rate is greater than about 1° C./min, and wherein said first temperature is between about 120° C. and about 350° C.;
(ii) holding for a first hold time at the first temperature, wherein said first hold time is between about 5 to about 300 minutes; and
(iii) cooling at a second rate to provide a nanoparticle PZT solution comprising a suspended plurality of perovskite PZT nanoparticles having a smallest dimension of between about 20 nm and about 1000 nm, wherein said second rate is greater than about 1° C./min.
16. The method of claim 1 , wherein the precursor solution includes about 10% to about 90%, by weight, of excess lead.
17. The method of claim 1 , wherein the precursor solution includes about 50% to about 90%, by weight, of excess lead.