Enhancement of light emission quantum yield in treated broad spectrum nanocrystals
Inorganic photoluminescent nanoparticles comprising a solid assembly comprising a first plurality of atoms from group II crystallized with a second plurality of atoms from group VI; at least one dimension of the assembly less than about 3.0 nm; and one or more organocarboxylate agents coupled to a surface that bounds the assembly, wherein the nanocrystal exhibits nanocrystal photoluminescence quantum yield of at least about 10%. Coupling to such surface comprises coating at least a portion of the nanocrystal being coated with the organocarboxylate agent, wherein the organocarboxylate agent is a carboxylic acid or the conjugate base of a carboxylic acid. The carboxylic acid can be is selected from formic acid, acetic acid, hexanoic acid, octanoic acid, oleic acid, and benzoic acid. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present invention.
1. A method of increasing photoluminescence quantum yield, the method comprising the steps of:
(a) providing a nanocrystal comprising a first plurality of atoms from group II and a second plurality of atoms from group VI; and
(b) treating the nanocrystal with a molar excess of one or more organocarboxylate agents for a time period and at a temperature sufficient to increase nanocrystal photoluminescence quantum yield, compared with the nanocrystal before treatment.
2. The method of claim 1 , wherein the organocarboxylate agent is a carboxylic acid.
3. The method of claim 2 , wherein the carboxylic acid is selected from formic acid, acetic acid, hexanoic acid, octanoic acid, oleic acid, and benzoic acid.
4. The method of claim 1 , wherein the organocarboxylate agent is the conjugate base of a carboxylic acid.
5. The method of claim 4 , wherein the conjugate base is a salt selected from sodium, potassium, calcium, and zinc of a carboxylic acid selected from formic acid, acetic acid, hexanoic acid, octanoic acid, oleic acid, and benzoic acid.
6. The method of claim 1 , wherein the organocarboxylate agent is formic acid or a salt thereof.
7. The method of claim 1 , further comprising cooling the solution and agent to a temperature of at most about 28° C.
8. The method of claim 1 , wherein the increase in nanocrystal photoluminescence quantum yield is at least double that of the nanocrystal before treatment.
9. The method of claim 1 , wherein the treated nanocrystal exhibits photoluminescence with a quantum yield of at least about 20%.
10. The method of claim 1 , wherein providing comprises the steps of:
(a) heating, to a temperature of greater than about 300° C., a reaction mixture comprising a C 4 to C 22 alkyl- or aryl-phosphonic acid and a source of atoms from group II in a molar ratio of from about 1:5 to about 1:1 Cd/Zn:phosphonic acid;
(b) adding to the reaction mixture an injection mixture comprising a C 2 to C 16 trialkyl- or triarylphosphine and a source of atoms from group VI; and
(c) decreasing the temperature of the reaction mixture to less than about 300° C.,
yielding a nanocrystal comprising a first plurality of atoms from group II and a second plurality of atoms from group VI.
11. A photoluminescent nanocrystal comprising:
(a) a solid assembly comprising a first plurality of atoms from group II crystallized with a second plurality of atoms from group VI;
(b) at least one dimension of the assembly less than about 3.0 nm; and
(c) one or more organocarboxylate agents coupled to a surface that bounds the assembly,
wherein the nanocrystal exhibits broad spectrum photoluminescence with quantum yield of at least about 10%,
wherein the organocarboxylate agent is a carboxylic acid selected from formic acid, acetic acid, hexanoic acid, actanoid acid, oleic acid, and benzoic acid, or
wherein the organocarboxylate agent is the conjugate base of a carboxylic acid.
12. The nanocrystal of claim 11 , wherein the group II atoms are selected from cadmium and zinc, and the group VI atoms are selected from selenium and sulfur.
13. The nanocrystal of claim 11 , further comprising a core of atoms within the assembly, the core comprising:
(a) a third plurality of atoms from group II crystallized with
(b) a fourth plurality of atoms from group VI,
wherein at least one of the third plurality is different from the first plurality or the fourth plurality is different from the second plurality.
14. The nanocrystal of claim 11 , wherein the carboxylic acid is selected from formic acid and acetic acid.
15. The nanocrystal of claim 11 , wherein the carboxylic acid is selected from hexanoic acid, octanoic acid, oleic acid, and benzoic acid.
16. The nanocrystal of claim 11 , wherein the conjugate base is a salt selected from sodium, potassium, calcium, and zinc of a carboxylic acid selected from formic acid and acetic acid.
17. The nanocrystal of claim 11 , wherein the conjugate base is a salt selected from sodium, potassium, calcium, and zinc of a carboxylic acid selected from hexanoic acid, octanoic acid, oleic acid, and benzoic acid.
18. The nanocrystal of claim 11 , wherein the organocarboxylate agent is formic acid or a salt thereof.
19. The nanocrystal of claim 11 , wherein the nanocrystal exhibits a photoluminescence quantum yield of at least double that of a nanocrystal without one or more organocarboxylate agents.
20. The nanocrystal of claim 11 , wherein the nanocrystal exhibits photoluminescence with a quantum yield of at least about 20%.