Luminescent nanoparticles and methods for their preparation

• US 20060057382A1
• Filed: 11/09/2004
• Published: 03/16/2006
• Est. Priority Date: 07/20/2001
• Status: Active Grant

• Current Assignee: Invitrogen Corp. (Thermo Fisher Scientific Incorporated)
• Original Assignee: Invitrogen Corp. (Thermo Fisher Scientific Incorporated)
• Inventors: Treadway, Joseph A., Zehnder, Donald A., Schrier, Marc D.
• Granted Patent: US 7,172,791 B2
• Time in Patent Office: Days
• US Class Current: 428/403
• CPC Class Codes: C09K 11/08 containing inorganic luminescent materials
• CPC Class Codes: C09K 11/0805 Chalcogenides
• CPC Class Codes: C09K 11/0811 with zinc or cadmium
• CPC Class Codes: C09K 11/54 containing zinc or cadmium
• CPC Class Codes: C09K 11/565 with zinc cadmium
• CPC Class Codes: C09K 11/883 with zinc or cadmium
• CPC Class Codes: Y10T 428/2984 Microcapsule with fluid core [includes liposome]
• CPC Class Codes: Y10T 428/2991 Coated
• CPC Class Codes: Y10T 428/2993 Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

Abstract

Methods for synthesizing luminescent nanoparticles and nanoparticles prepared by such methods are provided. The nanoparticles are prepared by a method in which an additive is included in the reaction mixture. The additive may be a Group 2 element, a Group 12 element, a Group 13 element, a Group 14 element, a Group 15 element, or a Group 16 element. In additions, a luminescent nanoparticle is provided that comprises a semiconductive core surrounded by an inorganic shell, an interfacial region and an additive present in the interfacial region or both the interfacial region and the shell.

Claims

1. A luminescent nanoparticle prepared according to a method comprising the steps of:

a) providing a semiconductive core;

b) admixing with the core

i. a first shell precursor,

ii. a second shell precursor,

iii. a solvent and

iv. an additive comprising an element selected from the group consisting of a Group 2 element, a Group 12 element, a Group 13 element, a Group 14 element, a Group 15 element, a Group 16 element, Fe, Nb, Cr, Mn, Co, Cu, and Ni,

to form a reaction dispersion; and

c) heating the reaction dispersion to a temperature for a period of time sufficient to induce formation of an inorganic shell on the semiconductive core.

2. The nanoparticle of claim 1, wherein the solvent and the additive are admixed with the core prior to addition of the first and second shell precursors and wherein step (c) is concurrent with the addition of the first and second shell precursors.

3. The nanoparticle of claim 1, wherein the semiconductive core comprises a material selected from the group consisting of:

a) a first element selected from Groups 2, 12, 13, or 14 and a second element selected from Group 16;

b) a first element selected from Group 13 and a second element selected from Group 15;

c) a Group 14 element; and

d) ternary and quaternary mixtures, compounds, and solid solutions thereof.

4. The nanoparticle of claim 3, wherein the semiconductive core comprises a material selected from the group consisting of MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, Al₂S₃, Al₂Se₃, Al₂Te₃, Ga₂S₃, Ga₂Se₃, Ga₂Te₃, In₂S₃, In₂Se₃, In₂Te₃, SnS, SnSe, SnTe, PbS, PbSe, PbTe, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, BP, Si, and Ge, and ternary and quaternary mixtures, compounds, and solid solutions thereof.

5. The nanoparticle of claim 4, wherein the semiconductive core comprises a material selected from the group consisting of CdSe, CdTe, CdS, ZnSe, InP, InAs, and PbSe, and ternary and quaternary mixtures, compounds, and solid solutions thereof.

6. The nanoparticle of claim 1, wherein the inorganic shell comprises a material selected from the group consisting of:

a) a first element selected from Groups 2, 12, 13, or 14 and a second element selected from Group 16;

b) a first element selected from Group 13 and a second element selected from Group 15; and

c) a Group 14 element.

7. The nanoparticle of claim 6, wherein the inorganic shell comprises a material selected from the group consisting of MgO, MgS, MgSe, MgTe, CaO, CaS, CaSe, CaTe, SrO, SrS, SrSe, SrTe, BaO, BaS, BaSe, BaTe, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, Al₂O₃, Al₂S₃, Al₂Se₃, Al₂Te₃, Ga₂O₃, Ga₂S₃, Ga₂Se₃, Ga₂Te₃, In₂O₃, In₂S₃, In₂Se₃, In₂Te₃, SiO₂, GeO₂, SnO, SnO₂, SnS, SnSe, SnTe, PbO, PbO₂, PbS, PbSe, PbTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, BP, and ternary and quaternary mixtures, compounds, and solid solutions thereof.

8. The nanoparticle of claim 7, wherein the inorganic shell comprises a material selected from the group consisting of CdSe, CdS, ZnSe, ZnS, CdO, ZnO, SiO₂, Al₂O₃, and ZnTe.

9. The nanoparticle of claim 1, wherein the semiconductive core comprises a material selected from the group consisting of CdSe, CdTe, CdS, ZnSe, InP, InAs, and PbSe and wherein the inorganic shell is selected from the group consisting of CdSe, CdS, ZnSe, ZnS, CdO, ZnO, SiO₂, Al₂O₃, and ZnTe, and ternary and quaternary mixtures, compounds, and solid solutions thereof.

10. The nanoparticle of claim 1, wherein the semiconductive core is CdSe or CdTe, the inorganic shell is ZnS and the additive is Cd, or the inorganic shell is CdS and the additive is Zn.

11. The nanoparticle of claim 1, wherein the solvent and the semiconductive core are admixed with the additive and the first shell precursor prior to the addition of the second shell precursor and wherein step (c) is concurrent with addition of the second shell precursor.

12. The nanoparticle of claim 1, wherein the solvent and the semiconductive core are admixed with the first shell precursor prior to the addition of the additive and the second shell precursor and wherein step (c) is concurrent with the addition of the second shell precursor.

13. A luminescent nanoparticle prepared according to a method comprising the steps of:

a) preparing a semiconductive core according to a method comprising adding a first amount of a first core precursor and a first amount of a second core precursor to form a reaction solution and reacting the first core precursor with the second core precursor under conditions which result in the formation of the semiconductive core and the presence of an amount of a first additive comprising unreacted first core precursor, second core precursor, or both first and second core precursor in the reaction solution;

b) heating the core to a temperature sufficient to induce formation of an inorganic shell on the core upon addition thereto of shell precursors;

c) admixing with the reaction solution a first shell precursor and a second shell precursor to form a reaction dispersion; and

d) maintaining the reaction dispersion at a temperature for a period of time sufficient to induce formation of an inorganic shell on the semiconductive core.

14. The nanoparticle in claim 13, wherein a second additive is combined with the reaction solution prior to or during step (b).

15. The nanoparticle in claim 14, wherein the second additive is a second amount of the first core precursor, the second core precursor or both the first and the second core precursors.

16. The nanoparticle in claim 14, wherein the second amount of the second additive is in the proportion of at least 5% of the amount of the added first core precursor, the added second core precursor or both the first and second core precursors.

17. The nanoparticle of claim 14, wherein the second additive is selected from the group consisting of a Group 2 element, a Group 12 element, a Group 13 element, a Group 14 element, a Group 15 element, a Group 16 element, Fe, Nb, Cr, Mn, Co, Cu, and Ni.

18. The nanoparticle of claim 14, wherein the first and second additives are the same or different.

19. A luminescent nanoparticle prepared according to a method comprising the steps of:

a) providing a semiconductive core;

b) heating the core to a temperature sufficient to induce formation of an inorganic shell on the core upon addition thereto of shell precursors

c) admixing with the core

i. a first shell precursor,

ii. a second shell precursor,

iii. a solvent and

iv. an additive comprising an element selected from the group consisting of a Group 2 element, a Group 12 element, a Group 13 element, a Group 14 element, a Group 15 element, a Group 16 element, Fe, Nb, Cr, Mn, Co, Cu, and Ni,

to form a reaction dispersion; and

d) maintaining the temperature of the reaction dispersion at a temperature for a period of time sufficient to form an inorganic shell on the semiconductive core.

20. The nanoparticle of claim 19, wherein the semiconductive core comprises a material selected from the group consisting of:

a) a first element selected from Groups 2, 12, 13, or 14 and a second element selected from Group 16;

b) a first element selected from Group 13 and a second element selected from Group 15;

c) a Group 14 element; and

d) ternary and quaternary mixtures, compounds, and solid solutions thereof.

21. The nanoparticle of claim 20, wherein the semiconductive core comprises a material selected from the group consisting of MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, Al₂S₃, Al₂Se₃, Al₂Te₃, Ga₂S₃, Ga₂Se₃, Ga₂Te₃, In₂S₃, In₂Se₃, In₂Te₃, SnS, SnSe, SnTe, PbS, PbSe, PbTe, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, BP, Si, and Ge, and ternary and quaternary mixtures, compounds, and solid solutions thereof.

22. The nanoparticle of claim 21, wherein the semiconductive core comprises a material selected from the group consisting of CdSe, CdTe, CdS, ZnSe, InP, InAs, and PbSe, and ternary and quaternary mixtures, compounds, and solid solutions thereof.

23. The nanoparticle of claim 19, wherein the inorganic shell comprises a material selected from the group consisting of:

a) a first element selected from Groups 2, 12, 13, or 14 and a second element selected from Group 16;

b) a first element selected from Group 13 and a second element selected from Group 15; and

c) a Group 14 element.

24. The nanoparticle of claim 23, wherein the inorganic shell comprises a material selected from the group consisting of MgO, MgS, MgSe, MgTe, CaO, CaS, CaSe, CaTe, SrO, SrS, SrSe, SrTe, BaO, BaS, BaSe, BaTe, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, Al₂O₃, Al₂S₃, Al₂Se₃, Al₂Te₃, Ga₂O₃, Ga₂S₃, Ga₂Se₃, Ga₂Te₃, In₂O₃, In₂S₃, In₂Se₃, In₂Te₃, SiO₂, GeO₂, SnO, SnO₂, SnS, SnSe, SnTe, PbO, PbO₂, PbS, PbSe, PbTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, BP, and ternary and quaternary mixtures, compounds, and solid solutions thereof.

25. The nanoparticle of claim 24, wherein the inorganic shell comprises a material selected from the group consisting of CdSe, CdS, ZnSe, ZnS, CdO, ZnO, SiO₂, Al₂O₃, and ZnTe.

26. The nanoparticle of claim 19, wherein the semiconductive core comprises a material selected from the group consisting of CdSe, CdTe, CdS, ZnSe, InP, InAs, and PbSe and wherein the inorganic shell is selected from the group consisting of CdSe, CdS, ZnSe, ZnS, CdO, ZnO, SiO₂, Al₂O₃, and ZnTe, and ternary and quaternary mixtures, compounds, and solid solutions thereof.

27. The nanoparticle of claim 19, wherein the semiconductive core is CdSe or CdTe, the inorganic shell is ZnS and the additive is Cd, or the inorganic shell is CdS and the additive is Zn.

28. A method of preparing a luminescent nanoparticle comprising the steps of:

a) providing a semiconductive core;

b) admixing with the core

i. a first shell precursor,

ii. a second shell precursor,

iii. a solvent and

iv. an additive comprising an element selected from the group consisting of a Group 2 element, a Group 12 element, a Group 13 element, a Group 14 element, a Group 15 element, a Group 16 element, Fe, Nb, Cr, Mn, Co, Cu, and Ni,

to form a reaction dispersion; and

c) heating the reaction dispersion to a temperature for a period of time sufficient to induce formation of an inorganic shell on the semiconductive core.

29. The method of claim 28, wherein the solvent and the additive are admixed with the core prior to addition of the first and second shell precursors and wherein step (c) is concurrent with the addition of the first and second shell precursors.

30. The method of claim 28, wherein the solvent and the semiconductive core are admixed with the additive and the first shell precursor prior to the addition of the second shell precursor and wherein step (c) is concurrent with addition of the second shell precursor.

31. The method of claim 28, wherein the solvent and the semiconductive core are admixed with the first shell precursor prior to the addition of the additive and the second shell precursor and wherein step (c) is concurrent with the addition of the second shell precursor.

32. A method of preparing a luminescent nanoparticle comprising the steps of:

a) preparing a semiconductive core according to a method comprising adding a first amount of a first core precursor and a first amount of a second core precursor to form a reaction solution and reacting the first core precursor with the second core precursor under conditions which result in the formation of the semiconductive core and the presence of an amount of a first additive comprising unreacted first core precursor, second core precursor, or both the first and second core precursors in the reaction solution;

b) heating the core to a temperature sufficient to induce formation of an inorganic shell on the core upon addition thereto of shell precursors;

c) admixing with the reaction solution a first shell precursor and a second shell precursor to form a reaction dispersion; and

d) maintaining the reaction dispersion at a temperature for a period of time sufficient to induce formation of an inorganic shell on the semiconductive core.

33. The method in claim 32, wherein a second additive is combined with the reaction solution prior to or during step (c).