Metal halide crystals having a nanotube structure and methods

Patent metadata

Field	Value
Publication number	US-10947119-B2
Application number	US-201816155231-A
Country	US
Kind code	B2
Filing date	Oct 9, 2018
Priority date	Oct 10, 2017
Publication date	Mar 16, 2021
Grant date	Mar 16, 2021

Abstract

Provided are organic metal halide crystals having a 1D nanotube structure. The metal halide crystals may have a unit cell that includes two or more face-sharing metal halide dimers. The metal halide crystals also may include organic cations. Methods of forming metal halide crystals having a 1D nanotube structure also are provided.

First claim

We claim:

1. A metal halide crystal comprising:
a 1D nanotube structure, and
a unit cell according to formula (I)—
R d a M c 2 X b   (I);

wherein R is an organic cation comprising at least one positively charged moiety,
a is 2 to 8,
M is a metal atom selected from the group consisting of Sn, Pb, Sb, Bi, Ag, Au, Pd, Pt, Mn, Fe, Co, Ni, Cu, and Zn,
c is the charge of the metal atom,
d is the charge of the organic cation,
X is a halide ion selected from the group consisting of Cl, Br, and I,
b is 5 to 12, and
2( c )+ a ( d )= b.

2. The metal halide crystal of claim 1 , wherein R comprises protonated hexamethylenetetramine (HMTA).

3. The metal halide crystal of claim 2 , wherein d is 1.

4. The metal halide crystal of claim 1 , wherein M is Pb.

5. The metal halide crystal of claim 1 , wherein X is Br.

6. The metal halide crystal of claim 1 , wherein R comprises protonated hexamethylenetetramine (HMTA), d is 1, a is 3, M is Pb, c is 2, X is Br, b is 7, and the unit cell of the metal halide crystal has the following formula:
(C 6 H 13 N 4 ) 3 Pb 2 Br 7 .

7. The metal halide crystal of claim 6 , wherein the metal halide crystal comprises six face-sharing lead bromide dimers of the formula Pb 2 Br 7 3− .

8. The metal halide crystal of claim 1 , wherein R is selected from the group consisting of—

and a combination thereof.

9. The metal halide crystal of claim 1 , wherein the metal halide crystal emits light in response to photo-excitation.

10. The metal halide crystal of claim 9 , wherein the light emitted by the metal halide crystal is white light.

11. The metal halide crystal of claim 1 , wherein the metal halide crystal has a photoluminescence quantum efficiency (PLQE) of about 7%.

12. The metal halide crystal of claim 1 , wherein the 1D nanotube structure comprises a single-wall structure, a multiple-wall structure, or a combination thereof.

13. The metal halide crystal of claim 1 , wherein the 1D nanotube structure comprises a metal halide tube having an inner portion and an outer portion, and the organic cations are located at (i) the inner portion of the metal halide tube, and (ii) the outer portion of the metal halide tube.

14. The metal halide crystal of claim 13 , wherein a ratio of the number of organic cations located at the inner portion of the metal halide tube to the outer portion of the metal halide tube is about 1:2.

15. A method of making the metal halide crystal of claim 1 having a 1D nanotube structure, the method comprising:
providing a liquid comprising a metal halide and an organic halide salt; and
contacting the liquid with a crystallizing agent to form the metal halide crystal having a 1D nanotube structure;
wherein the metal halide comprises a compound according to formula (II)—
MX e   (II);

wherein M is a metal atom selected from the group consisting of Sn, Pb, Sb, Bi, Ag, Au, Pd, Pt, Mn, Fe, Co, Ni, Cu, and Zn;
X is a halide ion selected from the group consisting of Cl, Br, and I; and
e is 1, 2, or 3.

16. The method of claim 15 , wherein the liquid comprises dimethylformamide (DMF).

17. The method of claim 15 , wherein M is Pb, X is Br, e is 2, and the metal halide has the following formula:
PbBr 2 .

18. The method of claim 15 , wherein the organic halide salt comprises hexamethylenetetramine hydrobromide.

19. The method of claim 15 , wherein the crystallizing agent comprises dichloromethane.

20. A metal halide crystal comprising:
a 1D nanotube structure, and
a unit cell according to the following formula—
(C 6 H 13 N 4 ) 3 Pb 2 Br 7 .

Assignees

• Univ Florida State Res Found

Inventors

• Ma Biwu
• Lin Haoran

Classifications

• C07D487/20 Primary

  Spiro-condensed systems · CPC title

• Y10T428/2975

  Tubular or cellular · CPC title

• Y10T428/2918

  including free carbon or carbide or therewith [not as steel] · CPC title

• Y10T428/2913

  Rod, strand, filament or fiber · CPC title

• B82Y30/00

  Nanotechnology for materials or surface science, e.g. nanocomposites · CPC title