Thiolated hydrophilic ligands for improved quantum dot reliability in resin films
The present invention provides nanostructure compositions and methods of producing nanostructure compositions. The nanostructure compositions comprise a population of nanostructures comprising thiol-functionalized ligands to increase the stability of the composition in thiol resins. The present invention also provides nanostructure films comprising a population of nanostructures comprising thiol-functionalized ligands and methods of making nanostructure films using these nanostructures.
1. A composition comprising:
(a) a core/shell nanostructure; and
(b) thiolated ligands bound to the surface of the nanostructure, wherein the thiolated ligands have the formula I:
wherein:
x is 10 to 20;
y is 1 to 10;
z is 0 or 1;
R 1A and R 1B independently are H or C 1-20 alkyl;
R 2 is C 1-20 alkyl;
R 3 is C 1-20 alkyl, C 3-8 cycloalkyl, or C 6-14 aryl; and
R 4 is —O—, C 1-20 alkyl, or amido.
2. The composition of claim 1 , wherein the nanostructure comprises a core selected from the group consisting of InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnSSe, InAs, InGaAs, and InAsP.
3. The composition of claim 1 , wherein the nanostructure comprises a core of InP.
4. The composition of claim 1 , wherein the nanostructure comprises at least one shell and the at least one shell comprises a mixture of at least two materials selected from the group consisting of zinc, sulfur, selenium, tellurium, and cadmium.
5. The composition of claim 1 , wherein R 1B is C 1-5 alkyl.
6. The composition of claim 1 , wherein R 2 is —CH 2 CH 2 —.
7. The composition of claim 1 , wherein the nanostructure in (a) comprises an InP core and two shells, and wherein in formula (I) x is 19, y is 3, R 1B is CH 3 , and R 2 is —CH 2 CH 2 —.
8. A nanostructure composition, comprising:
(a) at least one population of core/shell nanostructures, wherein between about 20 and about 100 mole percent of ligands in at least one population of nanostructures comprise a thiolated ligand bound to the nanostructure, wherein the thiolated ligand has the formula I:
wherein:
x is 10 to 20,
y is 1 to 10,
z is 0 or 1,
R 1A and R 1B independently are H or C 1-20 alkyl,
R 2 is C 1-20 alkyl,
R 3 is C 1-20 alkyl, C 3-8 cycloalkyl, or C 6-14 aryl, and
R 4 is —O—, C 1-20 alkyl, or amido; and
(b) at least one organic resin, wherein at least one organic resin is a thiol-functionalized resin.
9. The nanostructure composition of claim 8 , comprising between one and five populations of nanostructures.
10. The nanostructure composition of claim 8 , wherein the at least one population of nanostructures contains a core selected from the group consisting of InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnSSe, InAs, InGaAs, and InAsP.
11. The nanostructure composition of claim 8 , comprising between one and five organic resins.
12. The nanostructure composition of claim 8 , wherein at least one organic resin is a mercaptofunctional compound.
13. The nanostructure composition of claim 8 , wherein the at least one organic resin is selected from the group consisting of trimethylol-propane tri(3-mercaptopropionate), glycol di(3-mercapto-propionate), tris[25-(3-mercaptopropionyloxy)ethyl]isocyanurate, di-pentaerythritol hexa(3-mercaptopropionate), ethoxylated trimethylolpropane tri(3-mercaptopropionate), polycaprolactone tetra(3-mercaptopropionate), pentaerythritol tetramercaptoacetate, trimethylol-propane trimercaptoacetate, glycol dimercaptoacetate, and pentaerythritol tetrakis(3-mercaptopropionate).
14. The nanostructure composition of claim 8 , wherein at least one population of nanostructures in (a) comprises an InP core and at least two shells and the at least one organic resin is pentaerythritol tetrakis(3-mercaptopropionate).
15. The nanostructure composition of claim 8 , wherein the composition is stable for between about 1 day and about 3 years when stored at a temperature between about 10° C. and about 90° C.
16. A method of preparing the nanostructure composition of claim 8 , the method comprising:
(a) providing a composition comprising at least one population of core/shell nanostructures, wherein between about 20 and about 100 mole percent of ligands in the population of nanostructures comprise the thiolated ligand bound to the nanostructure; and
(b) admixing at least one organic resin with the composition of (a), wherein at least one organic resin is a thiol-functionalized resin.
17. A nanostructure film layer comprising:
(a) at least one population of core/shell nanostructures, wherein between about 20 and about 100 mole percent of ligands in the population of nanostructures comprise a thiolated ligand bound to the nanostructure, wherein the thiolated ligand has the formula I:
wherein:
x is 10 to 20;
y is 1 to 10;
z is 0 or 1;
R 1A and R 1B independently are H or C 1-20 alkyl;
R 2 is C 1-20 alkyl;
R 3 is C 1-20 alkyl, C 3-8 cycloalkyl, or C 6-14 aryl; and
R 4 is —O—, C 1-20 alkyl, or amido; and
(b) at least one organic resin, wherein at least one organic resin is a thiol-functionalized resin.
18. The nanostructure film layer of claim 17 , comprising between one and five populations of nanostructures.
19. The nanostructure film layer of claim 17 , wherein the at least one population of nanostructures contains a core selected from the group consisting of InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnSSe, InAs, InGaAs, and InAsP.
20. The nanostructure film layer of claim 17 , comprising between one and five organic resins.
21. The nanostructure film layer of claim 17 , wherein the at least one organic resin is selected from the group consisting of trimethylol-propane tri(3-mercaptopropionate), glycol di(3-mercapto-propionate), tris[25-(3-mercaptopropionyloxy)ethyl]isocyanurate, di-pentaerythritol hexa(3-mercaptopropionate), ethoxylated trimethylolpropane tri(3-mercaptopropionate), polycaprolactone tetra(3-mercaptopropionate), pentaerythritol tetramercaptoacetate, trimethylol-propane trimercaptoacetate, glycol dimercaptoacetate, and pentaerythritol tetrakis(3-mercaptopropionate).