Optoelectronic devices with organometal perovskites with mixed anions

Abstract

The invention provides an optoelectronic device comprising a mixed-anion perovskite, wherein the mixed-anion perovskite comprises two or more different anions selected from halide anions and chalcogenide anions. The invention further provides a mixed-halide perovskite of the formula (I) [A][B][X]3 wherein: [A] is at least one organic cation; [B] is at least one divalent metal cation; and [X] is said two or more different halide anions. In another aspect, the invention provides the use of a mixed-anion perovskite as a sensitizer in an optoelectronic device, wherein the mixed-anion perovskite comprises two or more different anions selected from halide anions and chalcogenide anions. The invention also provides a photosensitizing material for an optoelectronic device comprising a mixed-anion perovskite wherein the mixed-anion perovskite comprises two or more different anions selected from halide anions and chalcogenide anions.

1 - 87 . (canceled) 
     
     
         88 . An optoelectronic device comprising a mixed-anion perovskite, wherein the mixed-anion perovskite comprises two or more different anions selected from halide anions. 
     
     
         89 . An optoelectronic device according to  claim 88 , wherein the mixed-anion perovskite comprises a first cation, a second cation, and said two or more different anions selected from halide anions. 
     
     
         90 . An optoelectronic device according to  claim 89 , wherein the second cation is a divalent metal cation. 
     
     
         91 . An optoelectronic device according to  claim 90 , wherein the second cation is selected from Sn 2+  and Pb 2+ . 
     
     
         92 . An optoelectronic device according to  claim 89 , wherein the first cation is an organic cation. 
     
     
         93 . An optoelectronic device according to  claim 92 , wherein the organic cation is any of:
 an organic cation having the formula (R 1 R 2 R 3 R 4 N) + , wherein R 1  is hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, or unsubstituted or substituted aryl; R 2  is hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, or unsubstituted or substituted aryl; R 3  is hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, or unsubstituted or substituted aryl; and R 4  is hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, or unsubstituted or substituted aryl; and   an organic cation having the formula (R 5 R 6 N═CH—NR 7 R 8 ) + , wherein R 5  is hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, or unsubstituted or substituted aryl; R 6  is hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, or unsubstituted or substituted aryl; R 7  is hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, or unsubstituted or substituted aryl; and R 8  is hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, or unsubstituted or substituted aryl; and preferably has the formula (H 2 N═CH—NH 2 ) + .   
     
     
         94 . An optoelectronic device according to  claim 93 , wherein the organic cation is an organic cation having the formula (R 5 NH 3 ) + , wherein R 5  is hydrogen, or unsubstituted or substituted C 1 -C 20  alkyl. 
     
     
         95 . An optoelectronic device according to  claim 88 , wherein the mixed-anion perovskite has the formula [A][B][X] 3  wherein [A] is at least one cation, [B] is at least one cation, and [X] is two or more different halide anions, wherein one of the two or more different halide anions is iodide. 
     
     
         96 . An optoelectronic device according to  claim 88 , wherein the perovskite is a perovskite compound of the formula (I):
   [A][B][X] 3   (I)
   
       wherein:
 [A] is at least one organic cation; 
 [B] is at least one metal cation; and 
 [X] is said two or more different anions selected from halide anions. 
 
     
     
         97 . An optoelectronic device according to  claim 88 , wherein the perovskite is a mixed-halide perovskite of the formula (Ia)
   [A][B][X] 3   (Ia)
   
       wherein:
 [A] is at least one cation, comprising at least one organic cation of the formula (R 5 R 6 N═CH—NR 7 R 8 ) + , wherein: 
 (i) R 5  is hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, or unsubstituted or substituted aryl; 
 (ii) R 6  is hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, or unsubstituted or substituted aryl; 
 (iii) R 7  is hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, or unsubstituted or substituted aryl; and 
 (iv) R 8  is hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, or unsubstituted or substituted aryl; 
 [B] is at least one divalent metal cation; and 
 [X] is two or more different halide anions. 
 
     
     
         98 . An optoelectronic device according to  claim 88 , wherein the perovskite is a perovskite compound of formula (IIa):
   ABX 3z X′ 3(1−z)   (IIa)
   
       wherein:
 A is an organic cation of the formula (R 5 R 6 N═CH—NR 7 R 8 ) + , wherein: R 5 , R 6 , R 7  and R 8  are independently selected from hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, and unsubstituted or substituted aryl; 
 B is a metal cation; 
 X is a first halide anion; 
 X′ is a second halide anion which is different from the first halide anion; and 
 z is greater than 0 and less than 1. 
 
     
     
         99 . An optoelectronic device according to  claim 98 , wherein z is from 0.05 to 0.95. 
     
     
         100 . An optoelectronic device according to  claim 88 , wherein the perovskite is selected from CH 3 NH 3 PbBrI 2 , CH 3 NH 3 PbBrCl 2 , CH 3 NH 3 PbIBr 2 , CH 3 NH 3 PbICl 2 , CH 3 NH 3 PbClBr 2 , CH 3 NH 3 PbI 2 Cl, CH 3 NH 3 SnBrI 2 , CH 3 NH 3 SnBrCl 2 , CH 3 NH 3 SnF 2 Br, CH 3 NH 3 SnIBr 2 , CH 3 NH 3 SnICl 2 , CH 3 NH 3 SnF 2 I, CH 3 NH 3 SnClBr 2 , CH 3 NH 3 SnI 2 C 1  and CH 3 NH 3 SnF 2 Cl. 
     
     
         101 . An optoelectronic device according to  claim 98 , wherein the perovskite has the formula (H 2 N═CH—NH 2 )PbI 3z Br 3(1−z) . 
     
     
         102 . An optoelectronic device according to  claim 88 , wherein said optoelectronic device is an optoelectronic device selected from: a light-emitting device; a photodiode; a photomultiplier; a photo resistor; a photo detector; solid-state triode; a battery electrode; a transistor; and a laser. 
     
     
         103 . An optoelectronic device according to  claim 102 , wherein said optoelectronic device is selected from: a light-emitting diode; a phototransistor; a light-sensitive detector; and a diode injection laser. 
     
     
         104 . An optoelectronic device according to  claim 102 , wherein said optoelectronic device is a light-emitting device. 
     
     
         105 . An optoelectronic device according to  claim 104 , wherein said optoelectronic device is a light-emitting diode. 
     
     
         106 . An optoelectronic device comprising a perovskite of the formula (I)
   [A][B][X] 3   (I)
   
       wherein:
 [A] is at least one cation, comprising at least one organic cation of the formula (R 5 R 6 N═CH—NR 7 R 8 ) + , wherein: 
 (i) R 5  is hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, or unsubstituted or substituted aryl; 
 (ii) R 6  is hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, or unsubstituted or substituted aryl; 
 (iii) R 7  is hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, or unsubstituted or substituted aryl; and 
 (iv) R 8  is hydrogen, unsubstituted or substituted C 1 -C 20  alkyl, or unsubstituted or substituted aryl; 
 [B] is at least one divalent metal cation, wherein [B] comprises Pb 2+ ; and 
 [X] is iodide. 
 
     
     
         107 . An optoelectronic device according to  claim 106 , wherein the optoelectronic device is a light-emitting device.