Granted Patent B2

US 12,635,331 · App. 17/766,881 · Granted May 19, 2026

Inventors: Federico Koch (Heidelberg, DE); Christian Kasparek (Heidelberg, DE)

Assignee: Samsung Display Co., Ltd.

H10K50/121C09K11/06H10K85/654H10K85/6572H10K85/658C09K2211/1014C09K2211/1018C09K2211/1022H10K50/11H10K50/135H10K50/30H10K2101/10H10K2101/20H10K2101/30H10K2102/351

Abstract

Claims (191)

1 . 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 first 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) an emitter material S B , which has a lowermost excited singlet state energy level S1 S and a highest occupied molecular orbital HOMO(S B ) having an energy E HOMO (S B );

wherein the relations expressed by the following formulas (1) to (5) apply:

S 1 H >S 1 E   (1)

S 1 H >S 1 S   (2)

S 1 E >S 1 S   (3)

E HOMO ( E B )> E HOMO ( S B )  (4)

E HOMO ( E B )> E HOMO ( H B )  (5), and

wherein the TADF material E B comprises 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 35 ) 2 , C(R 35 ) 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 each other 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 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 -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 5S , 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 R 5S ;

R 5S is at each occurrence independently from each other 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 each other 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);

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.

2 . The organic electroluminescent device according to claim 1 , wherein at least one of the following formulas (6) and (7) applies:

0.2 eV≤ E HOMO ( E B )− E HOMO ( S B )≤0.8 eV  (6)

0.2 eV≤ E HOMO ( E B )− E HOMO ( H B )≤0.8 eV  (7).

3 . The organic electroluminescent device according to claim 1 , 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.

4 . The organic electroluminescent device according to claim 1 , wherein the relation expressed by formula (8) applies:

S 1 S >T 1 E   (8).

5 . The organic electroluminescent device according to claim 1 , wherein the mass ratio of the emitter material S B to TADF material E B (S B :E B ) is >1.

6 . The organic electroluminescent device according to claim 1 , 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.

7 . The organic electroluminescent device according to claim 1 , wherein the emitter material S B is selected from the group consisting of a fluorescence emitter and an organic TADF emitter, wherein the organic TADF emitter has a ΔE ST value, which corresponds to the energy difference between S1 S and T1 S , of less than 0.4 eV.

8 . The organic electroluminescent device according to claim 1 , wherein the relation expressed by formula (10a), (10b), or (10c) applies:

E HOMO ( H B )> E HOMO ( S B )  (10a)

E HOMO ( S B )> E HOMO ( H B )  (10b)

−0.1 eV≤ E HOMO ( H B )− E HOMO ( S B )≤0.1 eV  (10c).

9 . The organic electroluminescent device according to claim 1 , wherein the relation between a lowest unoccupied molecular orbital LUMO(E B ) having an energy E LUMO (E B ) and a lowest unoccupied molecular orbital LUMO(S B ) having an energy E LUMO (S B ), expressed by formula (11), applies:

E LUMO ( E B )> E LUMO ( S B )  (11).

10 . The organic electroluminescent device according to claim 1 , 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 the emitter material 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.

11 . The organic electroluminescent device according to claim 1 , wherein the light-emitting layer B comprises 0.1-10% by weight of the TADF material E B .

12 . The organic electroluminescent device according to claim 1 , wherein the device exhibits an emission maximum λ max (D) of 440 to 560 nm.

13 . A method for generating visible light comprising the steps of:

(i) providing an organic electroluminescent device according to claim 1 ; and

(ii) applying an electrical current to the organic electroluminescent device.

14 . A thermally activated delayed fluorescence (TADF) material E B in combination with at least one host material H B and at least one emitter material S B in a light-emitting layer for increasing the lifetime of the organic electroluminescent device,

wherein the TADF material E B comprises 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 35 ) 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 each other 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 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 -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 5S , 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 R 5S ;

R 5S is at each occurrence independently from each other 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 each other 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);

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.

15 . The TADF material E B in combination with at least one host material H B and at least one emitter material S B in a light-emitting layer of claim 14 , 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) a first 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) the emitter material S B has a lowermost excited singlet state energy level S1 S and a highest occupied molecular orbital HOMO(S B ) having an energy E HOMO (S B );

wherein the relations expressed by the following formulas (1) to (5) apply:

S 1 H >S 1 E   (1)

S 1 H >S 1 S   (2)

S 1 E >S 1 S   (3)

E HOMO ( E B )> E HOMO ( S B )  (4)

E HOMO ( E B )> E HOMO ( H B )  (5).

Assignments (2)

Priority Claims (2)

Continuity (1)

References Cited (23)