Method of semiconductor nanocrystal synthesis
View Patent ↗A method is described for the manufacture of semiconductor nanoparticles. Improved yields are obtained by use of a reducing agent or oxygen reaction promoter.
1. A method of producing nanoparticles comprising:
(a) mixing a first precursor, at least one ligand, and at least one coordinating solvent to form a first mixture;
(b) adding to the first mixture a chemical reducing agent selected from primary and secondary phosphines, wherein the chemical reducing agent, the at least one ligand, and the at least one coordinating solvent are different;
(c) heating the first mixture to a temperature that is sufficiently high to form nanoparticles when a second precursor is added;
(d) introducing a second precursor into the first mixture to form a second mixture thereby resulting in the formation of a plurality of nanoparticles; and
(e) cooling the second mixture to stop further growth of the nanoparticles.
2. The method of claim 1 wherein the coordinating solvent is selected from the group consisting of amines, alkyl phosphines, alkyl phosphine oxides, fatty acids, ethers, furans, phospho-acids, pyridines, alkenes, alkynes and combinations thereof.
3. The method of claim 2 wherein the coordinating solvent is at least 90% pure.
4. The method of claim 1 wherein the ligand is selected from the group consisting of phospho-acids, carboxylic acids, amines, amides, alcohols, ethers, alkenes, and alkynes.
5. The method of claim 4 wherein the ligand is a phosphonic acid.
6. The method of claim 5 wherein the phosphonic acid is selected from the group consisting of hexylphosphonic acid, octylphosphinic acid, and tetradecylphosphonic acid.
7. The method of claim 1 wherein the coordinating solvent further comprises a non-coordinating solvent.
8. The method of claim 7 wherein the non-coordinating solvent is an alkane.
9. The method of claim 7 wherein the ligand is selected from the group consisting of phospho-acids, carboxylic acids, amines, amides, alcohols, ethers, alkenes, and alkynes.
10. The method of claim 1 wherein the nanoparticles are semiconductive.
11. The method of claim 1 wherein the first precursor is selected from the group consisting of Group 2, 12, 13 and 14 element-containing compounds.
12. The method of claim 1 wherein the second precursor is selected from the group consisting of Groups 14, 15 and 16 element-containing compounds.
13. The method of claim 1 which further comprises producing a nanoparticle shell, wherein the shell surrounds the nanoparticle.
14. The method of claim 13 wherein the shell producing step comprises: (a′) mixing the nanoparticles with at least one coordinating solvent to form a third mixture; (b′) heating the third mixture to a temperature that is sufficiently high to form a shell on the nanoparticles when third and fourth precursors are added; (c′) introducing third and fourth precursors into the third mixture to form a fourth mixture thereby resulting in the formation of shells on a plurality of nanoparticles; and (d′) cooling the third mixture to stop further growth of the shell; wherein the method further comprises exposing the third or fourth mixture to a reaction promoter selected from the group consisting of oxygen and a reducing agent.
15. The method of claim 14 wherein an additive or additive precursor is included in step (a′).
16. The method of claim 1 , wherein the chemical reducing agent is dicyclohexylphosphine or diphenylphosphine.
17. The method of claim 1 wherein the ligand is a phosphonic acid.
18. A method of producing semiconductive nanoparticles having a valency “n”, comprising:
(a) mixing a first precursor having a valency “c”, at least one ligand, and at least one coordinating solvent to form a first mixture;
(b) adding to the first mixture a chemical reducing agent selected from primary and secondary phosphines, wherein the chemical reducing agent converts the valency of the first precursor to a valency “a”, wherein the chemical reducing agent, the at least one ligand, and the at least one coordinating solvent are different;
(c) heating the first mixture to a temperature that is sufficiently high to form semiconductive nanoparticles when a second precursor is added;
(d) introducing a second precursor into the first mixture to form a second mixture thereby resulting in the formation of a plurality of semiconductive nanoparticles; wherein the second precursor has a valency “b”, and wherein a+b=n and c+b≠n; and
(e) cooling the second mixture to stop further growth of the semiconductive nanoparticles.
19. The method of claim 18 wherein the coordinating solvent is at least 90% pure.