US2022352468A1PendingUtilityA1

Organic electroluminescent device emitting visible light

Assignee: CYNORA GMBHPriority: Oct 14, 2019Filed: Oct 13, 2020Published: Nov 3, 2022
Est. expiryOct 14, 2039(~13.2 yrs left)· nominal 20-yr term from priority
C09K 11/06C09K 2211/1018H01L 51/0067H01L 51/0072H01L 51/008H01L 51/5028H10K 85/658H10K 2101/20H10K 85/322H10K 50/121C09K 2211/1022C09K 2211/1014H10K 85/6572H10K 85/654H10K 2101/10H10K 2101/30H10K 2102/351H10K 50/30H10K 50/135H10K 50/11
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Claims

Abstract

The invention relates to an organic electroluminescent device comprising a light-emitting layer B comprising a host material HB, a thermally activated delayed fluorescence (TADF) material EB, and a depopulation agent SB.

Claims

exact text as granted — not AI-modified
1 - 16 . (canceled) 
     
     
         17 . An organic electroluminescent device comprising a light-emitting layer B comprising:
 (i) a host material H B , which has a lowermost excited singlet state energy level S1 H , a lowermost excited triplet state energy level T1 H , and a highest occupied molecular orbital HOMO(H B ) having an energy E HOMO (H B );   (ii) a thermally activated delayed fluorescence (TADF) material E B , which has a lowermost excited singlet state energy level S1 E , a lowermost excited triplet state energy level T1 E , and a highest occupied molecular orbital HOMO(E B ) having an energy E HOMO (E B ); and   (iii) a depopulation agent S B , which has a lowermost excited singlet state energy level S1 S , optionally a lowermost excited triplet state energy level T1 S , and a highest occupied molecular orbital HOMO(S B ) having an energy E HOMO (S B );   wherein E B  emits thermally activated delayed fluorescence;   and wherein the relations expressed by the following formulas (1) to (3) and either (4a) and (4b), or (5a) and (5b) apply:
     S 1 H   >S 1 E   (1)
 
     S 1 H   >S 1 S   (2)
 
     S 1 S   >S 1 E   (3)
 
     E   HOMO ( E   B )≤ E   HOMO ( H   B )  (4a)
 
   0.2 eV≤ E   HOMO ( S   B )− E   HOMO ( E   B )≤0.8 eV  (4b)
 
     E   HOMO ( H   B )≥ E   HOMO ( E   B )  (5a)
 
   0.2 eV≤ E   HOMO ( S   B )− E   HOMO ( H   B )≤0.8 eV  (5b).
 
   
     
     
         18 . The organic electroluminescent device according to  claim 17 , wherein the TADF material E B  has a ΔE ST  value, which corresponds to the energy difference between S1 E  and T1 E , of less than 0.4 eV. 
     
     
         19 . The organic electroluminescent device according to  claim 17 , wherein the mass ratio of the TADF material E B  to depopulation agent S B  (E B :S B ) is >1. 
     
     
         20 . The organic electroluminescent device according to  claim 17 , wherein the organic electroluminescent device is selected from the group consisting of an organic light emitting diode, a light emitting electrochemical cell, and a light-emitting transistor. 
     
     
         21 . The organic electroluminescent device according to  claim 17 , wherein the TADF material E B  is an organic TADF emitter or a combination of two or more organic TADF emitters. 
     
     
         22 . The organic electroluminescent device according to  claim 17 , wherein the depopulation agent S B  is an organic TADF emitter or a combination of two or more organic TADF emitters. 
     
     
         23 . The organic electroluminescent device according to  claim 17 , wherein the relation between the lowest unoccupied molecular orbital LUMO(E B ) of the TADF material E B  having an energy E LUMO (E B ) and the lowest unoccupied molecular orbital LUMO(S B ) of the depopulation agent S B  having an energy E LUMO (S B ) expressed by formula (7) applies:
     E   LUMO ( S   B )> E   LUMO ( E   B )  (7).
   
     
     
         24 . The organic electroluminescent device according to  claim 17 , wherein a relation expressed by formula (6a), (6b), or (6c) applies:
     E   HOMO ( E   B )> E   HOMO ( H   B )  (6a)
       E   HOMO ( H   B )> E   HOMO ( E   B )  (6b)
     −0.2 eV≤ E   HOMO ( H   B )− E   HOMO ( E   B )≤0.2 eV  (6c).
   
     
     
         25 . The organic electroluminescent device according to  claim 17 , wherein the light-emitting layer B comprises:
 (i) 39.8-98% by weight of the host compound H B ;   (ii) 0.1-50% by weight of the TADF material E B ; and   (iii) 0.1-50% by weight of depopulation agent S B ; and optionally   (iv) 0-60% by weight of one or more further host compounds H B2  differing from H B ; and optionally   (v) 0-60% by weight of one or more solvents; and optionally   (vi) 0-30% by weight of at least one further emitter molecule F.   
     
     
         26 . The organic electroluminescent device according to  claim 17 , wherein the light-emitting layer B comprises 1-8% by weight of the depopulation agent S B . 
     
     
         27 . The organic electroluminescent device according to  claim 17 , wherein the depopulation agent S B  has a ΔE ST  value, which corresponds to the energy difference between S1 S  and T1 S , of less than 0.4 eV. 
     
     
         28 . The organic electroluminescent device according to  claim 17 , wherein the TADF emitter E B  and/or the depopulation agent S B  comprises or consists of a structure according to Formula I-TADF 
       
         
           
           
               
               
           
         
         wherein:
 is at each occurrence independently from another 1 or 2; 
 p is at each occurrence independently from another 1 or 2; 
 X is at each occurrence independently from another selected from the group consisting of Ar EWG H, CN, and CF 3 ; 
 Z is at each occurrence independently from another selected from the group consisting of a direct bond, CR 3 R 4 , C═CR 3 R 4 , C═O, C═NR 3 , NR 3 , O, SiR 3 R 4 , S, S(O), and S(O) 2 ; 
 Ar EWG  is at each occurrence independently from another a structure according to one of Formulas IIa to IIk 
 
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           wherein # represents the binding site of the single bond linking Ar EWG  to the substituted central phenyl ring of Formula I-TADF; 
           R 1  is at each occurrence independently from another selected from the group consisting of hydrogen, deuterium, C 1 -C 5 -alkyl, wherein one or more hydrogen atoms are optionally substituted by deuterium, and C 6 -C 18 -aryl, which is optionally substituted with one or more substituents R 6 ; 
           R 2  is at each occurrence independently from another selected from the group consisting of hydrogen, deuterium, C 1 -C 5 -alkyl, wherein one or more hydrogen atoms are optionally substituted by deuterium, and C 6 -C 18 -aryl, which is optionally substituted with one or more substituents R 6 ; 
           R a , R 3 , and R 4  are at each occurrence independently from another selected from the group consisting of hydrogen, deuterium, N(R 5 ) 2 , OR 5 , 
           SR 5 , Si(R 5 ) 3 , CF 3 , CN, F, 
           C 1 -C 40 -alkyl, which is optionally substituted with one or more substituents R 5  and wherein one or more non-adjacent CH 2 -groups are optionally substituted by R 5 C═CR 5 , C≡C, Si(R 5 ) 2 , Ge(R 5 ) 2 , Sn(R 5 ) 2 , C═O, C═S, C═Se, C═NR 5 , P(═O)(R 5 ), SO, SO 2 , NR 5 , O, S, or CONR 5 ; 
           C 1 -C 40 -thioalkoxy, which is optionally substituted with one or more substituents R 5  and wherein one or more non-adjacent CH 2 -groups are optionally substituted by R 5 C═CR 5 , C≡C, Si(R 5 ) 2 , Ge(R 5 ) 2 , Sn(R 5 ) 2 , C═O, C═S, C═Se, C═NR 5 , P(═O)(R 5 ), SO, SO 2 , NR 5 , O, S, or CONR 5 ; 
           C 6 -C 60 -aryl, which is optionally substituted with one or more substituents R 5 ; and 
           C 3 -C 57 -heteroaryl, which is optionally substituted with one or more substituents R 5 ; 
           R 5  is at each occurrence independently from another selected from the group consisting of hydrogen, deuterium, N(R 6 ) 2 , OR 6 , SR 6 , Si(R 6 ) 3 , CF 3 , CN, F, 
           C 1 -C 40 -alkyl, which is optionally substituted with one or more substituents R 6  and wherein one or more non-adjacent CH 2 -groups are optionally substituted by R 6 C═CR 6 , C≡C, Si(R 6 ) 2 , Ge(R 6 ) 2 , Sn(R 6 ) 2 , C═O, C═S, C═Se, C═NR 6 , P(═O)(R 6 ), SO, SO 2 , NR 6 , O, S, or CONR 6 ; 
           C 6 -C 60 -aryl, which is optionally substituted with one or more substituents R 6 ; and 
           C 3 -C 57 -heteroaryl, which is optionally substituted with one or more substituents R 6 ; 
           R 6  is at each occurrence independently from another selected from the group consisting of hydrogen, deuterium, OPh, CF 3 , CN, F, 
           C 1 -C 5 -alkyl, wherein one or more hydrogen atoms are optionally, independently from each other substituted by deuterium, CN, CF 3 , or F; 
           C 1 -C 5 -alkoxy, wherein one or more hydrogen atoms are optionally, independently from each other substituted by deuterium, CN, CF 3 , or F; 
           C 1 -C 5 -thioalkoxy, wherein one or more hydrogen atoms are optionally, independently from each other substituted by deuterium, CN, CF 3 , or F; 
           C 6 -C 18 -aryl, which is optionally substituted with one or more C 1 -C 5 -alkyl substituents; 
           C 3 -C 17 -heteroaryl, which is optionally substituted with one or more C 6 -C 18 -aryl substituents and/or one or more C 1 -C 5 -alkyl substituents; 
           N(C 6 -C 18 -aryl) 2 ; 
           N(C 3 -C 17 -heteroaryl) 2 ; and 
           N(C 3 -C 17 -heteroaryl)(C 6 -C 18 -aryl); 
           R d  is at each occurrence independently from another selected from the group consisting of hydrogen, deuterium, N(R 5 ) 2 , OR 5 , 
           SR 5 , Si(R 5 ) 3 , CF 3 , CN, F, 
           C 1 -C 40 -alkyl, which is optionally substituted with one or more substituents R 5  and wherein one or more non-adjacent CH 2 -groups are optionally substituted by R 5 C═CR 5 , C≡C, Si(R 5 ) 2 , Ge(R 5 ) 2 , Sn(R 5 ) 2 , C═O, C═S, C═Se, C═NR 5 , P(═O)(R 5 ), SO, SO 2 , NR 5 , O, S, or CONR 5 ; 
           C 1 -C 40 -thioalkoxy, which is optionally substituted with one or more substituents R 5  and wherein one or more non-adjacent CH 2 -groups are optionally substituted by R 5 C═CR 5 , C≡C, Si(R 5 ) 2 , Ge(R 5 ) 2 , Sn(R 5 ) 2 , C═O, C═S, C═Se, C═NR 5 , P(═O)(R 5 ), SO, SO 2 , NR 5 , O, S, or CONR 5 ; 
           C 6 -C 60 -aryl, which is optionally substituted with one or more substituents R 5 ; and 
           C 3 -C 57 -heteroaryl which is optionally substituted with one or more substituents R 5 ; 
           wherein the substituents R a , R 3 , R 4 , or R 5  independently from each other may optionally form a mono- or polycyclic, aliphatic, aromatic, and/or benzo-fused ring system with one or more other substituents R a , R 3 , R 4 , or R 5 ; and 
           wherein the one or more substituents R d  independently from each other may optionally form a mono- or polycyclic, aliphatic, aromatic, and/or benzo-fused ring system with one or more other substituents R d . 
         
       
     
     
         29 . The organic electroluminescent device according to  claim 17 , wherein depopulation agent S B  comprises or consists of a structure according to Formula I-NRCT: 
       
         
           
           
               
               
           
         
         wherein: 
         o is 0 or 1; 
         m=1−o; 
         X 1  is N or B; 
         X 2  is N or B; 
         X 3  is N or B; 
         W is selected from the group consisting of Si(R 3S ) 2 , C(R 3S ) 2 , and BR 3S ; 
         each of R 1S , R 2S , and R 3S  is independently from each other selected from the group consisting of: 
         C 1 -C 5 -alkyl,
 which is optionally substituted with one or more substituents R 6S ; 
 
         C 6 -C 60 -aryl,
 which is optionally substituted with one or more substituents R 6S ; and 
 
         C 3 -C 57 -heteroaryl,
 which is optionally substituted with one or more substituents R 6S ; 
 
         each of R I , R II , R III , R IV , R V , R VI , R VII , R VIII , R IX , R X , and R XI  is independently from another selected from the group consisting of: 
         hydrogen, deuterium, N(R 5S ) 2 , OR 5S , Si(R 5S ) 3 , B(OR 5S ) 2 , OSO 2 R 5S , CF 3 , CN, halogen, 
         C 1 -C 40 -alkyl,
 which is optionally substituted with one or more substituents R 5S , and 
 wherein one or more non-adjacent CH 2 -groups are each optionally substituted by R 55 C═CR 5S , C≡C, Si(R 5S ) 2 , Ge(R 5S ) 2 , Sn(R 5S ) 2 , C═O, C═S, C═Se, C═NR 5S , P(═O)(R 5S ), SO, SO 2 , NR 5S , O, S, or CONR 5S ; 
 
         C 1 -C 40 -alkoxy,
 which is optionally substituted with one or more substituents R 5S , and 
 wherein one or more non-adjacent CH 2 -groups are each optionally substituted by R 5S C═CR 5S , C≡C, Si(R 5S ) 2 , Ge(R 5S ) 2 , Sn(R 5S ) 2 , C═O, C═S, C═Se, C═NR 5S , P(═O)(R 5S ), SO, SO 2 , NR 5S , O, S, or CONR 5S ; 
 
         C 1 -C 40 -thioalkoxy,
 which is optionally substituted with one or more substituents R 5S , and 
 wherein one or more non-adjacent CH 2 -groups are each optionally substituted by R 5S C═CR 5S , C≡C, Si(R 5S ) 2 , Ge(R 5S ) 2 , Sn(R 5S ) 2 , C═O, C═S, C═Se, C═NR 5S , P(═O)(R 5S ), SO, SO 2 , NR 5S , O, S, or CONR 5S ; 
 
         C 2 -C 40 -alkenyl,
 which is optionally substituted with one or more substituents R 5S , and 
 wherein one or more non-adjacent CH 2 -groups are each optionally substituted by R 5S C═CR 5S , C≡C, Si(R 5S ) 2 , Ge(R 5S ) 2 , Sn(R 5S ) 2 , C═O, C═S, C═Se, C═NR 5S , P(═O)(R 5S ), SO, SO 2 , NR 5S , O, S, or CONR 5S ; 
 
         C 2 -C 40 -alkynyl,
 which is optionally substituted with one or more substituents R 5S , and 
 wherein one or more non-adjacent CH 2 -groups are each optionally substituted by R 5S C═CR 5S , C≡C, Si(R 5S ) 2 , Ge(R 5S ) 2 , Sn(R 5S ) 2 , C═O, C═S, C═Se, C═NR 5S , P(═O)(R 5S ), SO, SO 2 , NR 5 S, O, S, or CONR 5S ; 
 
         C 6 -C 60 -aryl,
 which is optionally substituted with one or more substituents R 5S ; and 
 
         C 3 -C 57 -heteroaryl,
 which is optionally substituted with one or more substituents RSS; 
 
         R 5S  is at each occurrence independently from another selected from the group consisting of: hydrogen, deuterium, OPh, CF 3 , CN, F, 
         C 1 -C 5 -alkyl,
 wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF 3 , or F; 
 
         C 1 -C 5 -alkoxy,
 wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF 3 , or F; 
 
         C 1 -C 5 -thioalkoxy,
 wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF 3 , or F; 
 
         C 2 -C 5 -alkenyl,
 wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF 3 , or F; 
 
         C 2 -C 5 -alkynyl,
 wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF 3 , or F; 
 
         C 6 -C 18 -aryl,
 which is optionally substituted with one or more C 1 -C 5 -alkyl substituents; 
 
         C 3 -C 17 -heteroaryl,
 which is optionally substituted with one or more C 1 -C 5 -alkyl substituents; 
 
         N(C 6 -C 18 -aryl) 2 ; 
         N(C 3 -C 17 -heteroaryl) 2 ; and 
         N(C 3 -C 17 -heteroaryl)(C 6 -C 18 -aryl); 
         R 6S  is at each occurrence independently from another selected from the group consisting of hydrogen, deuterium, OPh, CF 3 , CN, F, 
         C 1 -C 5 -alkyl,
 wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF 3 , or F; 
 
         C 1 -C 5 -alkoxy,
 wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF 3 , or F; 
 
         C 1 -C 5 -thioalkoxy,
 wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF 3 , or F; 
 
         C 2 -C 5 -alkenyl,
 wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF 3 , or F; 
 
         C 2 -C 5 -alkynyl,
 wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF 3 , or F; 
 
         C 6 -C 18 -aryl,
 which is optionally substituted with one or more C 1 -C 5 -alkyl substituents; 
 
         C 3 -C 17 -heteroaryl,
 which is optionally substituted with one or more C 1 -C 5 -alkyl substituents; 
 
         N(C 6 -C 15 -aryl) 2 ; 
         N(C 3 -C 17 -heteroaryl) 2 ; and 
         N(C 3 -C 17 -heteroaryl)(C 6 -C 15 -aryl); 
         wherein two or more of the substituents selected from the group consisting of R I , R II , R III , R IV , R V , R VI , R VII , R VIII , R IX , R X , and R XI  that are positioned adjacent to another may optionally each form a mono- or polycyclic, aliphatic, aromatic, and/or benzo-fused ring system with another; and 
         wherein at least one of X 1 , X 2 , and X 3  is B and at least one of X 1 , X 2 , and X 3  is N. 
       
     
     
         30 . A method for generating visible light comprising the steps of:
 (i) providing an organic electroluminescent device according to  claim 17 ; and   (ii) applying an electrical current to the organic electroluminescent device.   
     
     
         31 . A thermally activated delayed fluorescence (TADF) material E B  in combination with at least one host material H B  and at least one depopulation agent S B  in a light-emitting layer for increasing the lifetime of the organic electroluminescent device. 
     
     
         32 . The TADF material E B  in combination with at least one host material H B  and at least one depopulation agent S B  in a light-emitting layer of  claim 31 , wherein:
 (i) the host material H B  has a lowermost excited singlet state energy level S1 H , a lowermost excited triplet state energy level T1 H , and a highest occupied molecular orbital HOMO(H B ) having an energy E HOMO (H B );   (ii) the TADF material E B  has a lowermost excited singlet state energy level S1 E , a lowermost excited triplet state energy level T1 E , and a highest occupied molecular orbital HOMO(E B ) having an energy E HOMO (E B ); and   (iii) the depopulation agent S B  has a lowermost excited singlet state energy level S1 S , optionally a lowermost excited triplet state energy level T1 S , and a highest occupied molecular orbital HOMO(S B ) having an energy E HOMO (S B );   wherein E B  emits thermally activated delayed fluorescence;   and wherein the relations expressed by the following formulas (1) to (3) and either (4a) and (4b), or (5a) and (5b) apply:
     S 1 H   >S 1 E   (1)
 
     S 1 H   >S 1 S   (2)
 
     S 1 S   >S 1 E   (3)
 
     E   HOMO ( E   B )≤ E   HOMO ( H   B )  (4a)
 
   0.2 eV≤ E   HOMO ( S   B )− E   HOMO ( E   B )≤0.8 eV  (4b)
 
     E   HOMO ( H   B )≥ E   HOMO ( E   B )  (5a)
 
   0.2 eV≤ E   HOMO ( S   B )− E   HOMO ( H   B )≤0.8 eV  (5b).

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