Aromatic heterocyclic derivative, material for organic eletroluminescent element, and organic electroluminescent element

Abstract

An organic EL device includes an anode, an emitting layer, an electron transporting zone and a cathode in this sequence, in which the electron transporting zone contains an aromatic heterocyclic derivative represented by a formula (1) below. In the formula (1), X 1 to X 3 are a nitrogen atom or CR 1 , and A is represented by a formula (2) below. In the formula (2), L 1 is s single bond or a linking group, and HAr is represented by a formula (3) below. In the formula (3), Y 1 is an oxygen atom, a sulfur atom or the like, and one of X 11 to X 18 is a carbon atom bonded to L 1 by a single bond and the rest of X 11 to X 18 are a nitrogen atom or CR 13 .

1 . An organic electroluminescence device comprising:
 an anode;   an emitting layer;   an electron transporting zone; and   a cathode in this sequence, wherein   the electron transporting zone comprises an aromatic heterocyclic derivative represented by a formula (1) below,   
       
         
           
           
               
               
           
         
         wherein: X 1  to X 3  are a nitrogen atom or CR 1 , with a proviso that at least one of X 1  to X 3  is a nitrogen atom; 
         R 1  independently represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms; 
         A is represented by a formula (2) below,
   (HAr) a -L 1 -  (2)
 
 
       
       wherein:
 HAr is represented by a formula (3) below; 
 a is an integer of 1 to 5; 
 when a is 1, L 1  is a single bond or a divalent linking group; 
 when a is in a range of 2 to 5, L 1  is a trivalent to hexavalent linking group and HAr is the same or different; 
 the linking group is a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, or a divalent to hexavalent residue induced from any one of a group formed by mutually bonding two or three of the substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms and the substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms; 
 the mutually bonded groups are the same or different, 
 
       
         
           
           
               
               
           
         
       
       wherein: X 11  to X 18  each are independently a nitrogen atom or CR 13 , with the proviso that X 13  or X 16  is a carbon atom bonded to L 1  by a single bond;
 Y 1  is an oxygen atom, a sulfur atom, SiR 11 R 12  or a silicon atom bonded to each of R 11  and L 1  by a single bond; 
 L 1  is bonded by one of a carbon atom at X 11  to X 18  and R 11  to R 12  and a silicon atom at Y 1 ; 
 R 11  and R 12  represent the same as R 1  in the formula (1); R 11  and R 12  are the same or different; 
 R 13  independently represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms; a plurality of R 13  are mutually the same or different; adjacent R 13  optionally bond to each other to form a ring; and 
 in the above formula (1), Ar 1  and Ar 2  each are independently represented by the formula (2), or represent a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms. 
 
     
     
         2 . The organic electroluminescence device according to  claim 1 , wherein
 in the formula (2), a is an integer of 1 to 3.   
     
     
         3 . The organic electroluminescence device according to  claim 1 , wherein
 in the formula (2), a is 1 or 2.   
     
     
         4 . The organic electroluminescence device according to  claim 1 , wherein
 in the formula (2), a is 1,   in the formula (2), L 1  is a linking group, and   the linking group is a divalent residue of a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a divalent residue of a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms.   
     
     
         5 . The organic electroluminescence device according to  claim 1 , wherein
 in the formula (2), a is 2 and L 1  is a linking group, and   the linking group is a trivalent residue of a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a trivalent residue of a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms.   
     
     
         6 . The organic electroluminescence device according to  claim 1 , wherein
 in the formula (3), Y 1  is an oxygen atom or a sulfur atom.   
     
     
         7 . The organic electroluminescence device according to  claim 1 , wherein
 in the formula (3), Y 1  is an oxygen atom or a sulfur atom, and   one of X 11  to X 18  is a carbon atom bonded to L 1  by a single bond and the rest of X 11  to X 18  are CR 13 .   
     
     
         8 . The organic electroluminescence device according to  claim 1 , wherein
 in the formula (1), two or three of X 1  to X 3  are a nitrogen atom.   
     
     
         9 . The organic electroluminescence device according to  claim 1 , wherein
 in the formula (2), L 1  is a divalent or trivalent residue induced from any one of benzene, biphenyl, terphenyl, naphthalene and phenanthrene.   
     
     
         10 . The organic electroluminescence device according to  claim 1 , wherein
 the electron transporting zone comprises a blocking layer, the blocking layer comprising the aromatic heterocyclic derivative represented by the formula (1).   
     
     
         11 . The organic electroluminescence device according to  claim 10 , further comprising:
 at least one of an electron injecting layer and an electron transporting layer between the blocking layer and the cathode, wherein   the at least one of the electron injecting layer and the electron transporting layer comprises at least one of an electron-donating dopant material and an organic metal complex.   
     
     
         12 . The organic electroluminescence device according to  claim 11 , wherein
 the electron-donating dopant material is at least one material selected from the group consisting of an alkali metal, an alkaline-earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halogenide, an alkaline-earth metal oxide, an alkaline-earth metal halogenide, a rare earth metal oxide and a rare earth metal halogenide, and   the organic metal complex is at least one complex selected from the group consisting of an organic metal complex comprising an alkali metal, an organic metal complex comprising an alkaline-earth metal, and an organic metal complex comprising a rare-earth metal.   
     
     
         13 . The organic electroluminescence device according to  claim 1 , wherein
 the emitting layer is in contact with the electron transporting zone comprising the aromatic heterocyclic derivative.   
     
     
         14 . The organic electroluminescence device according to  claim 1 , wherein
 the emitting layer comprises an anthracene derivative represented by a formula (20D) below,   
       
         
           
           
               
               
           
         
         wherein: Ar 11  and Ar 12  each independently represent a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms, a substituted or unsubstituted fused cyclic group having 10 to 30 ring atoms or a group formed by combining the monocyclic group and the fused cyclic group; 
         R 101  to R 108  each independently represent a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms, a substituted or unsubstituted fused cyclic group having 10 to 30 ring atoms, a group formed by combining the monocyclic group and the fused cyclic group, 
         a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 8 to 30 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted silyl group. 
       
     
     
         15 . The organic electroluminescence device according to  claim 1 , wherein
 the emitting layer comprises a fluorescent dopant material having a main peak wavelength of 500 nm or less.   
     
     
         16 . An organic electroluminescence device comprising:
 an anode;   an emitting layer;   an electron transporting zone; and   a cathode in this sequence, wherein   the electron transporting zone comprises an aromatic heterocyclic derivative represented by any one of formulae below   
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         17 . The organic electroluminescence device according to  claim 16 , wherein
 the electron transporting zone comprises a blocking layer, the blocking layer comprising the aromatic heterocyclic derivative.   
     
     
         18 . The organic electroluminescence device according to  claim 17 , further comprising:
 at least one of an electron injecting layer and an electron transporting layer between the blocking layer and the cathode, wherein   the at least one of the electron injecting layer and the electron transporting layer comprises at least one of an electron-donating dopant material and an organic metal complex.   
     
     
         19 . The organic electroluminescence device according to  claim 18 , wherein
 the electron-donating dopant material is at least one material selected from the group consisting of an alkali metal, an alkaline-earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halogenide, an alkaline-earth metal oxide, an alkaline-earth metal halogenide, a rare earth metal oxide and a rare earth metal halogenide, and   the organic metal complex is at least one complex selected from the group consisting of an organic metal complex comprising an alkali metal, an organic metal complex comprising an alkaline-earth metal, and an organic metal complex comprising a rare-earth metal.   
     
     
         20 . The organic electroluminescence device according to  claim 16 , wherein
 the emitting layer is in contact with the electron transporting zone comprising the aromatic heterocyclic derivative.   
     
     
         21 . The organic electroluminescence device according to  claim 16 , wherein
 the emitting layer comprises an anthracene derivative represented by a formula (20D) below,   
       
         
           
           
               
               
           
         
       
       wherein: Ar 11  and Ar 12  each independently represent a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms, a substituted or unsubstituted fused cyclic group having 10 to 30 ring atoms or a group formed by combining the monocyclic group and the fused cyclic group;
 R 101  to R 108  each independently represent a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms, a substituted or unsubstituted fused cyclic group having 10 to 30 ring atoms, a group formed by combining the monocyclic group and the fused cyclic group, 
 a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 8 to 30 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted silyl group. 
 
     
     
         22 . The organic electroluminescence device according to  claim 16 , wherein
 the emitting layer comprises a fluorescent dopant material having a main peak wavelength of 500 nm or less.   
     
     
         23 . The organic electroluminescence device according to  claim 16 , wherein
 the aromatic heterocyclic derivative comprised in the electron transporting zone is represented by any one of formulae below