Organic-inorganic hybrid perovskites, devices, and methods
View Patent ↗Provided herein are organic-inorganic hybrid-perovskites, including metal halide perovskites having a 1D crystal structure. The metal halide perovskites may be luminescent. The metal halide perovskites may include a dopant, including an emitter dopant. Methods of forming metal halide perovskites, and devices including the metal halide perovskites also are provided.
1. A metal halide perovskite comprising:
a 1D crystal structure comprising a unit cell according to formula (I)—
RMX 4 (I);
wherein M is a metal atom selected from Pb, Sn, Cu, Ge, Mn, Co, Bi, Sb, or Eu;
X is a halide ion selected from Cl, Br, or I; and
R is an organic cation comprising at least one secondary ammonium cation, at least one tertiary ammonium cation, or a combination thereof.
2. The metal halide perovskite of claim 1 , wherein the organic cation is N, N′-dimethylethane-1,2-diammonium:
3. The metal halide perovskite of claim 2 , wherein M is Pb, X is Cl, and the unit cell has the following formula:
(C 4 N 2 H 14 )PbCl 4 .
4. The metal halide perovskite of claim 2 , wherein M is Pb, X is Br, and the unit cell has the following formula:
(C 4 N 2 H 14 )PbBr 4 .
5. The metal halide perovskite of claim 2 , wherein M is Pb, X is I, and the unit cell has the following formula:
(C 4 N 2 H 14 )PbI 4 .
6. The metal halide perovskite of claim 1 , wherein the 1D crystal structure further comprises a dopant at a ratio of about 0.995:0.005 to about 0.90:0.1 (metal atom:dopant), as determined by X-ray fluorometer.
7. The metal halide perovskite of claim 6 , wherein the dopant comprises Mn 2+ ions, Eu 3+ ions, Pr 3+ ions, or a combination thereof.
8. The metal halide perovskite of claim 6 , wherein the photoluminescence quantum efficiency (PLQE) of the metal halide perovskite is at least 25%.
9. The metal halide perovskite of claim 1 , wherein the organic cation is a compound according to formula (A):
wherein each of R 1 -R 6 is independently selected from hydrogen or a monovalent C 1 -C 20 hydrocarbyl, and R 7 is a divalent C 1 -C 20 hydrocarbyl or a divalent C 6 -C 20 aryl.
10. The metal halide perovskite of claim 9 , wherein R 7 is a divalent, unsubstituted C 1 -C 4 hydrocarbyl; R 2 , R 3 , R 5 , and R 6 are hydrogen; each of R 1 and R 4 is independently a monovalent, unsubstituted C 1 -C 3 hydrocarbyl, and the organic cation is a compound according to the following formula (D):
11. The metal halide perovskite of claim 1 , wherein R 7 is a divalent, unsubstituted C 6 aryl; each of R 2 , R 3 , R 5 , and R 6 is hydrogen; each of R 1 and R 4 is independently a monovalent, unsubstituted C 1 -C 3 hydrocarbyl; and the organic cation is a compound according to the following formula (G):
12. The metal halide perovskite of claim 1 , wherein the organic cation is a compound according to the following formula (H):
wherein each of R 1 and R 3 is independently selected from a divalent C 1 -C 20 hydrocarbyl, and each of R 2 , R 4 , and R 5 is independently selected from hydrogen or a monovalent C 1 -C 20 hydrocarbyl.
13. The metal halide perovskite of claim 12 , wherein R 2 is hydrogen; each of R 4 and R 5 is independently a monovalent, unsubstituted C 1 -C 3 hydrocarbyl; each of R 1 and R 3 is independently a divalent, unsubstituted C 2 -C 4 hydrocarbyl; and the organic cation is a compound according to the following formula (I):
14. The metal halide perovskite of claim 12 , wherein R 2 is a divalent C 2 -C 4 hydrocarbyl substituted with a secondary amine; each of R 4 and R 5 is independently a monovalent, unsubstituted C 1 -C 3 hydrocarbyl; each of R 1 and R 3 is independently a divalent, unsubstituted C 2 -C 4 hydrocarbyl; and the organic cation is a compound according to the following formula (J):
15. The metal halide perovskite of claim 1 , wherein the organic cation is a compound according to the following formula (K):
wherein R 1 and R 5 are independently selected from a monovalent C 1 -C 20 hydrocarbyl or hydrogen, R 2 and R 4 are independently selected from a divalent C 1 -C 20 hydrocarbyl, and R 3 is a divalent C 1 -C 20 hydrocarbyl or a divalent C 6 -C 20 aryl.
16. The metal halide perovskite of claim 15 , wherein R 1 and R 5 are independently selected from an unsubstituted, monovalent C 1 -C 3 hydrocarbyl; R 2 , R 3 , and R 4 are independently selected from an unsubstituted, divalent C 2 -C 4 hydrocarbyl, and the organic cation has a structure according to the following formula (L):
17. The metal halide perovskite of claim 1 , wherein the organic cation is a compound according to the following formula (M):
wherein n is 0 or 1, each of R 1 -R 4 and R 8 is independently selected from a divalent C 1 -C 20 hydrocarbyl, and each of R 5 -R 7 is independently selected from a monovalent C 1 -C 20 hydrocarbyl or hydrogen.
18. The metal halide perovskite of claim 17 , wherein n is 1, R 1 -R 4 are independently selected from an unsubstituted, divalent C 1 -C 4 hydrocarbyl; R 8 is an unsubstituted, divalent C 1 -C 3 hydrocarbyl; R 5 -R 7 are independently selected from an unsubstituted, monovalent C 1 -C 3 hydrocarbyl; and the organic cation is a compound according to the following formula (N):
19. The metal halide perovskite of claim 17 , wherein n is 0, R 1 -R 3 are independently selected from an unsubstituted, divalent C 1 -C 4 hydrocarbyl; R 5 -R 7 are independently selected from an unsubstituted, monovalent C 1 -C 3 hydrocarbyl; and the organic cation is a compound according to the following formula (O):
20. The metal halide perovskite of claim 1 , wherein the organic cation is a compound according to the following formula (P):
wherein m is 0 or 1, n is 1-4, each R 1 is independently selected from a divalent C 1 -C 20 hydrocarbyl, and each R 2 is independently selected from a monovalent C 1 -C 20 hydrocarbyl or hydrogen.
21. The metal halide perovskite of claim 20 , wherein m is 0, n is 3, R 2 is independently selected from an unsubstituted, monovalent C 1 -C 3 hydrocarbyl, and the organic cation is a compound according to the following formula (Q):
22. The metal halide perovskite of claim 1 , wherein the organic cation comprises a compound according to one of structures (1)-(10):
23. An optoelectronic device comprising the metal halide perovskite of claim 1 , wherein the metal halide perovskite is a light emitting material.
24. The device of claim 23 , wherein the metal halide perovskite emits light that is white, blue, green, yellow, orange, or red.
25. The device of claim 23 , wherein the optoelectronic device is a light emitting diode, a light emitting electrochemical cell, or an optically pumped laser.