Low-dimensional hybrid post-perovskites for high efficiency white-light emission

Patent metadata

Field	Value
Publication number	US-12084608-B2
Application number	US-201917052887-A
Country	US
Kind code	B2
Filing date	Jun 14, 2019
Priority date	Jun 15, 2018
Publication date	Sep 10, 2024
Grant date	Sep 10, 2024

Abstract

The present invention relates to a new type of low-dimensional hybrid post-perovskites for high efficiency white light emission. More precisely, the invention relates to a one dimensional post-perovskite of formula A a M m X x ·yH 2 O wherein A is a cis- or trans-2,5-dialkylpiperazine derivative bearing C 1 -C 3 linear or branched alkyl groups, M is one or more metal, X one or more halogen, 0<a<5, 1<m<2, 2<x<12, 0<y. The invention also relates to material and luminescent device comprising the same and methods of preparation of the of low-dimensional hybrid post-perovskites.

First claim

The invention claimed is:

1. A one dimensional hybrid post-perovskite of formula I:
A a M m X x ,y H 2 O  Formula I

wherein
a=1,
m=1,
x=4,
0≤y,
A represents a cis- or trans-piperazine of formula II:

in which R 1 and R 2 , identical or different, represent a C 1 -C 3 linear or branched alkyl chain,
M represents one or more metal atoms chosen from the group consisting of Pb, Sn, Ge, Sb, Bi, Mn and Zn and mixture thereof,
X represents one or more halogen atoms.

2. The one dimensional hybrid post-perovskite according to claim 1 , wherein A represents trans-2,5-dimethylpiperazine.

3. The one dimensional hybrid post-perovskite according to claim 1 , wherein X is chosen from F, Cl, Br and I and mixtures thereof.

4. The one dimensional hybrid post-perovskite according to claim 1 , wherein M is chosen from Pb and Sn.

5. A method for producing the one dimensional hybrid post-perovskite of claim 1 , comprising a step of mixing the reagents:
one or more M or MX 2 ,
a piperazine, and
one or more aqueous HX to obtain an aqueous mixture,

the piperazine, M and X being defined as above.

6. The method according to claim 5 , further comprising a step of heating and agitating the mixture.

7. The method according to claim 6 , wherein the heating temperature is from 20° C. to 250° C.

8. The method according to claim 6 , wherein the agitation is carried over a period from 10 seconds to 100 hours.

9. A luminescent material comprising a one dimensional hybrid post-perovskite according to claim 1 .

10. A luminescent device comprising a one dimensional hybrid post-perovskite material according to claim 9 .

11. A one dimensional hybrid post-perovskite TDMPPbBr 4 crystal form wherein the XRPD pattern at Bragg angles (2θ) shows peaks of values 7.92°, 12.52°, 14.60°, 20.24°, 22.50°, 23.20°, 28.22°, 28.80°, wherein TDMP stands for trans-2,5-dimethylpiperazine.

12. A one dimensional hybrid post-perovskite TDMPPbCl 4 crystal form wherein the XRPD pattern at Bragg angles (2θ) shows peaks of values 8.15°, 12.86°, 18.18°, 20.74°, 23.02°, 23.75°, 28.87°, 29.45°, 32.75°, 33.78°, 34.78°, 35.28°, wherein TDMP stands for trans-2,5-dimethylpiperazine.

13. A one dimensional hybrid post-perovskite TDMPPbI 4 crystal form wherein the XRPD pattern at Bragg angles (2θ) shows peaks of values 7.68°, 12.13°, 13.73°, 21.74°, 22.42°, 27.79°, 32.83°, wherein TDMP stands for trans-2,5-dimethylpiperazine.

14. The one dimensional hybrid post-perovskite according to claim 1 , configured for a luminescent device comprising a LED including display or backlighting, LASER, wireless light fidelity.

15. The method according to claim 7 , wherein the agitation is carried over a period from 10 seconds to 100 hours.

16. The one dimensional hybrid post-perovskite according to claim 1 , wherein A represents a cis- or trans-piperazine of formula II in which R 1 and R 2 represent methyl groups.

17. The one dimensional hybrid post-perovskite according to claim 1 , wherein M is a mixture of metals M 1 and M 2 , wherein M 1 and M 2 are different and represents each one metal atom chosen from the group consisting of Pb, Sn, Ge, Sb, Bi, Mn and Zn and mixture thereof.

18. The one dimensional hybrid post-perovskite according to claim 17 , wherein, in formula I, M m represents M 1 m1 M 2 m2 , wherein 0<m1<1, 0<m2<1 and m1+m2=m=1.

19. The one dimensional hybrid post-perovskite according to claim 18 , wherein m1 is in a range from 0.9000 to 0.9999 and wherein m2 is in a range from 0.0001 to 0.1000.

20. The one dimensional hybrid post-perovskite according to claim 17 , wherein M 1 is Pb or Sn and wherein M 2 is Mn.

21. The luminescent device according to claim 10 , wherein the luminescent device comprises at least one LED.

22. The luminescent device according to claim 10 , wherein the luminescent device is chosen from the group consisting of a display, a backlighting unit, a LASER, a wireless light fidelity and a large area display.

23. A one dimensional hybrid post-perovskite TDMPPb 0.9997 Mn 0.0003 Br 4 crystal form wherein the XRPD pattern at Bragg angles (2θ) shows peaks of values 8.10°, 12.71°, 20.45°, 22.68°, 23.40°, 28.40°, 28.98°, wherein TDMP stands for trans-2,5-dimethylpiperazine.

Assignees

• Centre Nat Rech Scient
• Univ Nantes

Inventors

• Gautier Romain
• Massuyeau Florian
• Paris Michael

Classifications

• H10H20/8512

  Wavelength conversion materials · CPC title

• H10K85/30

  Coordination compounds · CPC title

• C09K2211/188

  of other metals not provided for in one of the previous groups · CPC title

• C09K2211/1044

  containing two nitrogen atoms as heteroatoms · CPC title

• C07F7/24

  Lead compounds · CPC title