TERNARY AND QUATERNARY NANOCRYSTALS, PROCESSES FOR THEIR PRODUCTION AND USES THEREOF
(19)AUSTRALIAN PATENT OFFICE(54) Title TERNARY AND QUATERNARY NANOCRYSTALS, PROCESSES FOR THEIR PRODUCTION ANDUSES THEREOF (51)6 International Patent Classification(s) B82B ooi/oo C30B 029/52 B82B 003/00(21) Application No: 2003294200 (22) Application Date: 2003.12.16(87) WIPONo: WO04/054923 (30) Priority Data (31) Number (32) Date 10/321,278 2002.12.16 (33) Country US(43) Publication Date : 2004.07.09 (43) Publication Journal Date : 2004.08.19(71) Applicant(s) AGENCY FOR SCIENCE, 1 bCHNOLOGY AND RESEARCH(72) Inventor(s) HAN, Mingyong; ZHONG, Xinhua;KNOLL, Wolfgang (H) Application NoAU2003294200 A1(19)AUSTRALIAN PATENT OFFICE(54) Title TERNARY AND QUATERNARY NANOCRYSTALS, PROCESSES FOR THEIR PRODUCTION ANDUSES THEREOF (51)6 International Patent Classification(s) B82B ooi/oo C30B 029/52 B82B 003/00(21) Application No: 2003294200 (22) Application Date: 2003.12.16(87) WIPONo: WO04/054923 (30) Priority Data (31) Number (32) Date 10/321,278 2002.12.16 (33) Country US(43) Publication Date : 2004.07.09 (43) Publication Journal Date : 2004.08.19(71) Applicant(s) AGENCY FOR SCIENCE, 1 bCHNOLOGY AND RESEARCH(72) Inventor(s) HAN, Mingyong; ZHONG, Xinhua;KNOLL, Wolfgang The present invention relates to nanocrystals consisting of a homogeneous ternary or quaternary alloy having the composition M1<SUB>1-x</SUB>M2<SUB>x</SUB>A and M1<SUB>1-x</SUB>M2<SUB>x</SUB>A<SUB>y</SUB>B<SUB>1-y</SUB>, respectively, a process for its production, as well as to uses of such nanocrystals such as as short wavelength light-emitting devices, and in the detection of analytes, in particular biomolecules. What is claimed: 1. A nanocrystal consisting of a homogeneous ternary alloy having the composition Mli. xM2xA, wherein a) MI and M2 are independently selected from an element of subgroup lib, subgroup VIIa, subgroup VIIIa, subgroup Ib or main group II of the periodic system of the elements (PSE), when A represents an element of the main group VI of thePSE, or b) M1 and M2 are both selected from an element of the main group (III) of the PSE, when A represents an element of the main group (V) of the PSE, obtainable by a process comprising i) forming a binary nanocrystal M1A by heating a reaction mixture containing the element MI in a form suitable for the generation of a nanocrystal to a suitable temperature T1,STDC0882 adding at this temperature the element A in a form suitable for the generation of a nanocrystal, heating the reaction mixture for a sufficient period of time at a temperature suitable for forming said binary nanocrystalM1A and then allowing the reaction mixture to cool, and ii) reheating the reaction mixture, without precipitating or isolating the formed binary nanocrystal M1A, to a suitable temperature T2, adding to the reaction mixture at this temperature a sufficient quantity of the element M2 in a form suitable for the generation of a nanocrystal, then heating the reaction mixture for a sufficient period of time at a temperature suitable for forming said ternary nanocyrstal Mll-xM2xA and then allowing the reaction mixture to cool to room temperature, and isolating the ternary nanocrystal MljM2xA.
2. The nanocrystal of claim 1 with 0.001 < x < 0.999.
3. The nanocrystal of claim 1 or 2 with 0.01 < x < 0.99 4. The nanocrystal of any of claims 1 to 3 with 0.5 < x < 0.95.
5. The nanocrystal of any of claims 1 to 4, wherein the elements MI and M2 are independently selected from the group consisting of Zn, Cd, Hg, Mn, Fe, Co, Ni, Cu,Ag, and Au.
6. The nanocrystal of any of claims 1 to 5, wherein the element A is selected from the group consisting of S, Se, Te. <Desc/Clms Page number 31> 7. The nanocrystal of any of claims 1 to 6 having the composition ZnXcdl-xse or ZnXCdl-xS.
8. The nanocrystal of claim 7 with 0.10 < x < 0.9 9. The nanocrystal of claim 8 with 0.15 < x < 0.85.
10. The nanocrystal of claim 9 with 0.2 < x < 0.8.
11. A process of producing a nanocrystal consisting of a homogeneous ternary alloy having the composition Mll-xM2xA with 0.001 < x < 0.999, wherein a) MI and M2 are independently selected from an element of the subgroup lib, subgroup VIIa, subgroup Villa, subgroup Ib or main group II of the periodic system of the elements (PSE), when A represents an element of the main group VI of the PSE, or b) MI and M2 are both selected from an element of the main group (III) of the PSE, when A represents an element of the main group (V) of the PSE, said process comprising i) forming a binary nanocrystal M1A by heating a reaction mixture containing the element M1 in a form suitable for the generation of a nanocrystal to a suitable temperature T1,STDC0892 adding at this temperature the element A in a form suitable for the generation of a nanocrystal, heating the reaction mixture for a sufficient period of time at a temperature suitable for forming said binary nanocrystal M1A and then allowing the reaction mixture to cool, and ii) reheating the reaction mixture, without precipitating or isolating the formed binary nanocrystal M1A, to a suitable temperature T2, adding to the reaction mixture at this temperature a sufficient quantity of the element M2 in a form suitable for the generation of a nanocrystal, then heating the reaction mixture for a sufficient period of time at a temperature suitable for forming said ternary nanocrystal Mli-xM2xA and then allowing the reaction mixture to cool to room temperature, and isolating the ternary nanocrystal Mll-xM2xA.
12. The process of claim 11, wherein the reaction mixture in i) is allowed to cool to a temperature below 100 C after formation of the binary nanocrystal M1A.
13. The process of claim 11 or 12 with 0.001 < x < 0.999.
14. The process of any of claims 11 to 13 with 0.1 < x < 0.95. <Desc/Clms Page number 32> 15. The process of any of claims 11 to 14, wherein the elements M1 and M2 are independently selected from the group consisting of Zn, Cd, Hg, Mn, Fe, Co, Ni, Cu,Ag, and Au.
16. The process of any of claims 11 to 15, wherein the element A is selected from the group consisting of S, Se, and Te.
17. The process of any of claims 11 to 16 wherein the nanocrystal has the composition ZnXCdl?xSe or ZnxCdz?XS.
18. The process of claim 17 with 0.10 < x < 0.9.
19. The process of claim 18 with 0.15 < x < 0.85.
20. The process of claim 19 with 0.2 < x < 0.8.
21. The process of any of claims 11 to 20, wherein the reaction mixture in i) is heated to a temperature TI between 150 C and 400 C.
22. The process of any of claims 11 to 21, wherein the reaction mixture in ii) is heated to a temperature between 200 C and 400 C.
23. The process of any of claims 11 to 22, wherein in ii) a second quantity of the elementA is added for the formation of the ternary nanocrystal.
24. A process of producing a nanocrystal consisting of a homogeneous ternary alloy having the composition Mll-xM2xA with 0.001 < x < 0.999, wherein a) MI and M2 are independently selected from an element of the subgroup lib, subgroup VIIa, subgroup VIIIa, subgroup Ib or main group II of the periodic system of the elements (PSE), when A represents an element of the main group VI of thePSE, or b) M1 and M2 are both selected from an element of the main group (III) of thePSE, when A represents an element of the main group (V) of the PSE, said process comprising i) providing a reaction mixture containing the elements M1, M2 and A each in a form suitable for the generation of a nanocrystal, <Desc/Clms Page number 33> ii)STDC0255 heating the reaction mixture for a sufficient period of time at a temperature suitable for forming said ternary nanocrystal M1M2A and then allowing the reaction mixture to cool, and iii) isolating the ternary nanocrystal MljM2xA.
25. The process of claim 24, wherein the reaction mixture in i) is formed by preparing a solution containing none or one of the two elements M1 or M2 in a form suitable for the generation of a nanocrystal, heating the solution for a suitable time, then adding to the solution the element A in a form suitable for the generation of a nanocrystal and then adding the other of the two elements MI or M2 in a form suitable for the generation of a nanocrystal.
26. The process of claim 24, wherein the reaction mixture in i) is formed by preparing a solution containing the element A in a form suitable for the generation of a nanocrystal, heating the solution for a suitable time, then adding to the solution the two elements M1 or M2 in a form suitable for the generation of a nanocrystal.
27. The process of claim 24, wherein the reaction mixture in i) is formed by preparing a solution containing the both the elements M1 and M2 in a form suitable for the generation of a nanocrystal, heating the solution for a suitable time, then adding to the solution the element A in a form suitable for the generation of a nanocrystal.
28. The process of any of claims 24 to 27, wherein the reaction mixture in ii) is heated to a temperature between 260 C and 340 C.
29. The process of claim 28, wherein the reaction mixture is heated to a temperature between 270 C and 340 C 30. The process of any of claims 24 to 27 or claim 23, wherein the solution in i) containing either one of or both of the elements M1 or M2 or the element A is heated to a temperature between 260 C and 340 C.
31. The process of claim 30, wherein the solution is heated to 310 C.
32. The process of any of claims 24 to 31, wherein the reaction is carried out in an inert atmosphere. <Desc/Clms Page number 34> 33. A nanocrystal consisting of a homogeneous quarternary alloy having the composition Mlj-xM2xAyBi. y, wherein a) MI and M2 are independently selected from an element of the subgroup lib, subgroup VIIa, subgroup VIIIa, subgroup Ib or main group II of the periodic system of the elements (PSE), when A and B both represent an element of the main group VI of the PSE, or b) MI and M2 are independently selected from an element of the main group (III) of the PSE, when A and B both represent an element of the main group (V) of thePSE, obtainable by a process comprising i) providing a reaction mixture containing the elements M1, M2, A and B each in a form suitable for the generation of a nanocrystal, ii)STDC0451 heating the reaction mixture for a sufficient period of time at a temperature suitable for forming said quarternary nanocrystal M11-xM2xAyB1-y and then allowing the reaction mixture to cool, and iii) isolating the quarternary nanocrystal Mll-xM2xAyBl-y 34. The nanocrystal of claim 33, wherein M1 and M2 are independently selected from the group consisting of Zn, Cd, Hg, Mn, Fe, Co, Ni, Cu, Ag, and Au.
35. The nanocrystal of claim 33 or 34 with 0. 001 < x < 0.999 and with 0.001 < y < 0.999.
36. A method of producing a nanocrystal consisting of a homogeneous quarternary alloy having the composition Mll-xM2xAyBl-y with 0.001 < x < 0.999 and 0.001 < y < 0.999, wherein a) Ml and M2 are independently selected from an element of the subgroup lib, subgroup VIIa, subgroup VIIIa, subgroup Ib or main group II of the periodic system of the elements (PSE), when A and B both represent an element of the main group VI of the PSE, or b) MI and M2 are independently selected from an element of the main group (III) of the PSE, when A and B both represent an element of the main group (V) of thePSE, obtainable by a process comprising i) providing a reaction mixture containing the elements M1, M2, A andB each in a form suitable for the generation of a nanocrystal, ii)STDC0338 heating the reaction mixture for a sufficient period of time at a temperature suitable for forming said quarternary nanocrystals M1l?xM2xAyB1-y and then allowing the reaction mixture to cool, and iii) isolating the quarternary nanocrystal a Mll-xM2xAyBl-yb <Desc/Clms Page number 35> 37.STDC0698 A process of producing a nanocrystal consisting of a homogeneous quarternary alloy having the composition MlxM2xAyBi-y with 0.001 < x < 0.999 and 0.001 < y < 0.999, wherein a) MI and M2 are independently selected from an element of the subgroup lib, subgroup VIIa, subgroup VIIIa, subgroup Ib or main group II of the periodic system of the elements (PSE), when A and B both represent an element of the main group VI of the PSE, or b) M1 and M2 are independently selected from an element of the main group (III) of the PSE, when A and B both represent an element of the main group (V) of the PSE, wherein said process comprises i)STDC0811 forming a ternary nanocrystal M1AB by heating a reaction mixture containing the element M1 in a form suitable for the generation of a nanocrystal to a suitable temperature T1, adding at this temperature the elements A and B in a form suitable for the generation of a nanocrystal, heating the reaction mixture for a sufficient period of time at a temperature suitable for forming said ternary nanocrystal M1AB and then allowing the reaction mixture to cool and ii) reheating the reaction mixture, without precipitating or isolating the formed ternary nanocrystal M1AB, to a suitable temperature T2, adding to the reaction mixture at this temperature a sufficient quantity of the element M2 in a form suitable for the generation of a nanocrystal,STDC0322 then heating the reaction mixture for a sufficient period of time at a temperature suitable for forming said quarternary nanocyrstal Mll-xM2xAyBl-y and then allowing the reaction mixture to cool to room temperature, and isolating the quarternary nanocrystal Mlj-xM2xAyBi. y.
38. A nanocrystal as defined in any of claims 1 to 10 or 33 to 35 conjugated to a molecule having binding affinity for a given analyte.
39. The nanocrystal of claim 38, wherein the molecule having binding affinity for a given analyte has binding affinity to a biomolecule.
40. The nanocrystal of claim 39, wherein the molecule having binding affinity for an analyte is a protein, a peptide, a compound having features of an immunogenic hapten, a nucleic acid, a carbohydrate or an organic molecule.
41. The nanocrystal of claim 40, wherein the nanocrystal is conjugated to said molecule having binding activity for an analyte via a linking agent. <Desc/Clms Page number 36> 42. The nanocrystal of any of claims 1 to 10,33 to 35 or 38 to 41 incorporated into a plastic bead.
43. A detection kit containing a nanocrystal as defined in any of claims 1 to 10,33 to 35 or 38 to 42.
44. The use of a nanocrystal as defined in any of claims 1 to 10,33 to 35 or 38 to 42 for the detection of an analyte.
45. A method of synthesizing a colloidal binary M1A nanocrystal comprising (a) Combining a metal MI selected from the subgroup lib, subgroup VIIa, subgroup VIIIa or subgroup Ib of the PSE with a ligand for said metal, and a coordinating solvent to form a metal complex; and (b) mixing an elemental chalcogenic precursor with the metal complex at a temperature sufficient to form nanocrystals.
46. The method of claim 45 wherein the metal MI is selected from the group consisting ofZn, Cd, Hg, Mn, Fe, Co, Ni, and Cu.
47. A process of producing a nanocrystal consisting of a homogeneous ternary alloy having the composition Mll-xM2xA with 0.001 < x < 0.999, wherein a) Ml and M2 are independently selected from an element of the subgroup lib, subgroup VIIa, subgroup VIIIa, subgroup Ib or main group II of the periodic system of the elements (PSE), when A represents an element of the main group VI of thePSE, or b) Ml and M2 are both selected from an element of the main group (III) of thePSE, when A represents an element of the main group (V) of the PSE, said process comprising heating core-shell nanocrystals at their alloying point or a temperature above said alloying point for a sufficient period of time.