Organic light-emitting diodes with fluorescent and phosphorescent emitters

Abstract

A light emitting device includes a first electrode, a hole transporting layer in contact with the first electrode, a second electrode, an electron transporting layer in contact with the second electrode; and an emissive layer between the hole transporting layer and the electron transporting layer. The emissive layer includes a phosphorescent emitter, a fluorescent emitter, and a host, and the phosphorescent emitter harvests electrogenerated excitons and transfers energy to the fluorescent emitter.

1 . A light emitting device comprising:
 a first electrode;   a hole transporting layer in contact with the first electrode;   a second electrode;   an electron transporting layer in contact with the second electrode; and   a single emissive layer between the hole transporting layer and the electron transporting layer, the emissive layer comprising a phosphorescent emitter, a fluorescent emitter, and a host, wherein the phosphorescent emitter harvests electrogenerated excitons and transfers energy to the fluorescent emitter;   wherein the phosphorescent emitter comprises a luminophore comprising a six-membered chelation ring.   
     
     
         2 .- 6 . (canceled) 
     
     
         7 . The light emitting device of  claim 1 , wherein the light emitting device is a fluorescent organic light emitting device. 
     
     
         8 . (canceled) 
     
     
         9 . The light emitting device of  claim 1 , wherein the phosphorescent emitter comprises a compound of General Formula I: 
       
         
           
           
               
               
           
         
         wherein:
 each of Y 1a , Y 1b , and Y 1c  is independently O, NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 , wherein each of R 3  and R 4  is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R 3  and R 4  together form C═O, wherein each of R 3  and R 4  is independently optionally linked to an adjacent ring structure, thereby forming a cyclic structure; 
 each of Y 2a , Y 2b , Y 2c , and Y 2d  is independently N, NR 5 , or CR 6 , wherein each R 5  and R 6  is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, or arylalkenyl; 
 each of Y 3a , Y 3b , Y 3c , Y 3d , Y 4a , Y 4b , Y 4c , and Y 4d  is independently N, O, S, NR 7 , CR 8 , wherein each R 7  and R 8  is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, aminoalkoxy, haloalkyl, arylalkyl, or arylalkenyl; or Z(R 9 ) 2 , wherein Z is C or Si, and wherein each R 9  is independently hydrogen, halogen, hydroxyl, thiol, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, or arylalkenyl; 
 each of m and n is independently 1 or 2; and 
 each   independently represents partial or full unsaturation of the ring with which it is associated. 
 
       
     
     
         10 . The light emitting device of  claim 9 , wherein:
 m is 2   n is 2; and   one of the following conditions (i) to (iii) is satisfied:   (i) M is Pt or Pd; at least one of Y 1a  and Y 1c  is independently NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 ; Y 2b  and Y 2c  are C; and Y 3b  and Y 4b  are N;   (ii) M is Ir or Rh; Y 1a  is NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 ; Y 2b  is C; and Y 3b , Y 2c  and Y 4b  are N; or   (iii) M is Au; Y 1b  is NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 ; Y 2b , Y 2c  and Y 4b  are C; and Y 3b  is N.   
     
     
         11 . (canceled) 
     
     
         12 . (canceled) 
     
     
         13 . The light emitting device of  claim 9 , wherein each of R 3  and R 4  is independently linked to an adjacent ring structure. 
     
     
         14 . The light emitting device of  claim 9 , wherein one of the following conditions (i) to (iii) is satisfied:
 M is Pt or Pd; at least one of Y 1b  and Y 1c  is independently NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 , wherein R 3  is covalently linked to at least one of Y 2a , Y 2d , Y 3d , and Y 4d  to form a cyclic structure; and at least of one of Y 2a , Y 2d , Y 3d  and Y 4d  is C;   (ii) M is Ir or Rh; Y 1b  is NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 , wherein R 3  is covalently linked to at least one of Y 2a  and Y 3d  to form a cyclic structure; and at least of one of Y 2a  and Y 3d  is C;   (iii) M is Au; at least of one of Y 2a  and Y 3d  is C; and Y 1b  is NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 , wherein R 3  is covalently linked to at least one of Y 2a  and Y 3d  to form a cyclic structure.   
     
     
         15 . (canceled) 
     
     
         16 . (canceled) 
     
     
         17 . The light emitting device of  claim 1 , wherein the phosphorescent emitter comprises a compound of General Formula II: 
       
         
           
           
               
               
           
         
         wherein:
 M is Ir, Rh, Pt, Os, or Ru; 
 each of R 1  and R 2  is independently hydrogen, halogen, hydroxyl, nitro, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, or arylalkenyl; 
 each of Y 1a , Y 1b , Y 1c , Y 1d , and Y 1e  is independently O, NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 , wherein each of R 3  and R 4  is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R 3  and R 4  together form C═O, wherein each of R 3  and R 4  is independently optionally linked to an adjacent ring structure, thereby forming a cyclic structure; 
 each of Y 2a , Y 2b , Y 2c , and Y 2d  is independently N, NR 5 , or CR 6 , wherein each of R 5  and R 6  is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, or arylalkenyl; 
 each of Y 3a , Y 3b , Y 3c , Y 3d , Y 4a , Y 4b , Y 4c , and Y 4d  is independently N, O, S, NR 7 , CR 8 , wherein each of R 7  and R 8  is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, or arylalkenyl; or Z(R 9 ) 2 , wherein Z is C or Si, and wherein each R 9  is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, or arylalkenyl; 
 in each of each of Y 5a , Y 5b , Y 5c , Y 5d , Y 6a , Y 6b , Y 6c , and Y 6d  is independently N, O, S, or C 8 ; 
 each of m and n is independently 1 or 2; and 
 each   independently represents partial or full unsaturation of the ring with which it is associated. 
 
       
     
     
         18 . The light emitting device of  claim 17 , wherein:
 M is Ir or Rh;   m is 2;   Y 2b  and Y 2c  are C;   Y 3b  and Y 4b  are N; and   at least one of Y 1b  and Y 1c  is NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 .   
     
     
         19 . The light emitting device of  claim 17 , wherein each of R 3  and R 4  is independently linked to an adjacent ring structure. 
     
     
         20 . The light emitting device of  claim 17 , wherein:
 M is Ir or Rh;   at least of one of Y 2a , Y 2d , Y 3d  and Y 4d  is C; and   at least one of Y 1b  and Y 1c  is NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 , wherein R 3  is covalently linked to at least one of Y 2a , Y 2d , Y 3d  and Y 4d , thereby forming a cyclic structure.   
     
     
         21 . The light emitting device of  claim 1 , wherein the phosphorescent emitter is a compound of General Formula III: 
       
         
           
           
               
               
           
         
         wherein:
 M is a metal cation with two positive charges selected from Pt (II) and Pd (II); 
 each E 1 , E 2 , and E 3  independently represents O, NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 , wherein each of R 3  and R 4  is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R 3  and R 4  together form C═O, wherein each of R 3  and R 4  is independently optionally linked to a C or N, thereby forming a cyclic structure; 
 each C independently represents a substituted or unsubstituted aromatic ring or heterocyclic group wherein a carbon atom is coordinated to M; and 
 each N independently represents a substituted or unsubstituted heterocyclic group wherein a nitrogen atom coordinated to M. 
 
       
     
     
         22 . The light emitting device of  claim 1 , wherein the phosphorescent emitter is a compound of General Formula IV: 
       
         
           
           
               
               
           
         
         wherein:
 M is a metal cation with three positive charges selected from Au (III) and Ag (III); 
 each E 1 , E 2 , and E 3  independently represents O, NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 , wherein each R 3  and R 4  is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R 3  and R 4  together form C═O, wherein each of R 3  and R 4  is independently optionally linked to a C or N, thereby forming a cyclic structure; 
 each C independently represents a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to M; and 
 
         N represents a substituted or unsubstituted heterocyclic group wherein a nitrogen atom is coordinated to M. 
       
     
     
         23 . The light emitting device of  claim 1 , wherein the phosphorescent emitter is a compound of General Formula V: 
       
         
           
           
               
               
           
         
         wherein:
 M is a metal cation with one positive charge selected from Ir (I) and Rh (I); 
 each E 1 , E 2 , and E 3  independently represents O, NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 , wherein each of R 3  and R 4  is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R 3  and R 4  together form C═O, wherein each of R 3  and R 4  is independently optionally linked to a C or N, thereby forming a cyclic structure; 
 C represents a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to M; and 
 each N independently represents a substituted or unsubstituted heterocyclic group wherein a nitrogen atom is coordinated to M. 
 
       
     
     
         24 . The light emitting device of  claim 1 , wherein the phosphorescent emitter is a compound of General Formula VI: 
       
         
           
           
               
               
           
         
         wherein:
 M is a metal cation with three positive charges selected from Ir (III), Rh (III), Co (III), Al (III), and Ga (III); 
 each of E 1 , E 2 , E 3 , and E 4  independently represents O, NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 , wherein each of R 3  and R 4  is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R 3  and R 4  together form C═O, wherein each of R 3  and R 4  is independently optionally linked to a C or N, thereby forming a cyclic structure; 
 each C independently represents a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to M; and 
 each N independently represents a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom coordinated to the metal. 
 
       
     
     
         25 . The light emitting device of  claim 1 , wherein the phosphorescent emitter is a compound of one of General Formulas VII and VIII: 
       
         
           
           
               
               
           
         
         wherein:
 M is a metal cation with three positive charges selected from Ir (III), Rh (III), Co (III), Al (III), or Ga (III); 
 each of E 1 , E 2 , E 3 , E 4 , and E 5  independently represents O, NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 , wherein each of R 3  and R 4  is independently hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, hydroxyl, halogen, thiol, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R 2  and R 3  together form C═O, wherein each of R 3  and R 4  is independently optionally linked to a C or N, thereby forming a cyclic structure; 
 each C independently represents a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to M; and 
 each N independently represents a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom coordinated to M. 
 
       
     
     
         26 . The light emitting device of  claim 1 , wherein the phosphorescent emitter is a compound of General Formula IX: 
       
         
           
           
               
               
           
         
         wherein:
 M is a metal cation with four positive charges selected from Pd (IV) and Pt (IV); 
 each of E 1 , E 2 , E 3 , and E 4  independently represents O, NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 , wherein each of R 3  and R 4  is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R 3  and R 4  together form C═O, wherein each of R 3  and R 4  is independently optionally linked to a C or N, thereby forming a cyclic structure; 
 each C independently represents a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to M; and 
 
         each N independently represents a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom coordinated to M. 
       
     
     
         27 . The light emitting device of  claim 1 , wherein the phosphorescent emitter is a compound of General Formula X: 
       
         
           
           
               
               
           
         
         wherein:
 M is a metal cation with four positive charges selected from Pd (IV) and Pt(IV); 
 each of E 1 , E 2 , E 3 , E 4 , and E 5  independently represents O, NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 , wherein each of R 3  and R 4  is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R 3  and R 4  together form C═O, wherein each of R 3  and R 4  is independently optionally linked to a C or N, thereby forming a cyclic structure; 
 each C independently represents a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to M; and 
 
         each N independently represents a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom is coordinated to M. 
       
     
     
         28 . The light emitting device of  claim 1 , wherein the phosphorescent emitter is a compound of General Formula XI: 
       
         
           
           
               
               
           
         
         wherein:
 M is a metal cation with two positive charges selected from Ru (II) and Os (II); 
 each of E 1 , E 2 , E 3 , E 4 , and E 5  independently represents O, NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 , wherein each of R 3  and R 4  is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R 3  and R 4  together form C═O, wherein each of R 3  and R 4  is independently optionally linked to a C or N, thereby forming a cyclic structure; 
 each C independently represents a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to M; and 
 each N independently represents a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom is coordinated to M. 
 
       
     
     
         29 . The light emitting device of  claim 1 , wherein the phosphorescent emitter is a compound of General Formula XII: 
       
         
           
           
               
               
           
         
         wherein:
 M is a metal cation with two positive charges selected from Ru (II) and Os (II); 
 each of E 1 , E 2 , E 3 , and E 4  independently represents O, NR 3 , CR 3 R 4 , S, AsR 3 , BR 3 , PR 3 , P(O)R 3 , or SiR 3 R 4 , wherein each of R 3  and R 4  is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R 3  and R 4  together form C═O, wherein each of R 3  and R 4  is independently optionally linked to a C or N, thereby forming a cyclic structure; 
 each C independently represents a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to M; and 
 each N independently represents a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom is coordinated to M. 
 
       
     
     
         30 . The light emitting device of  claim 1 , wherein the fluorescent emitter comprises one of the following compounds: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein:
 each of R 1l , R 2l , R 3l , R 4l , R 5l , R 6l , R 7l  and R 8l  is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric, or any conjugate or combination thereof, and 
 each of Y a , Y b , Y c , Y d , Y e , Y f , Y g , Y h , Y i , Y j , Y k , Y l , Y m , Y n , Y o , and Y p  is independently C, N or B; and 
 each of U a , U b  and U c  is independently CH 2 , CRR, C═O, SiRR, GeH 2 , GeRR, NH, NR, PH, PR, RP═O, AsR, RAs═O, O, S, S═O, SO 2 , Se, Se═O, SeO 2 , BH, BR, RBi═O, BiH, or BiR, wherein each R is independently is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric, or any conjugate or combination thereof.