Organic photosensitive devices using subphthalocyanine compounds

Abstract

An organic photosensitive optoelectronic device, having a donor-acceptor heterojunction of a donor-like material and an acceptor-like material and methods of making such devices is provided. At least one of the donor-like material and the acceptor-like material includes a subphthalocyanine, a subporphyrin, and/or a subporphyrazine compound; and/or the device optionally has at least one of a blocking layer or a charge transport layer, where the blocking layer and/or the charge transport layer includes a subphthalocyanine, a subporphyrin, and/or a subporphyrazine compound.

1 . An organic photosensitive optoelectronic device, comprising an anode, a cathode, and a donor-acceptor heterojunction between the anode and the cathode, the heterojunction comprising a donor-like material and an acceptor-like material, wherein at least one of the donor-like material and the acceptor-like material comprises a subphthalocyanine, a subporphyrin, and/or a subporphyrazine compound; and/or the device optionally comprises at least one of a blocking layer or a charge transport layer, wherein the blocking layer and/or the charge transport layer comprises a subphthalocyanine, a subporphyrin, and/or a subporphyrazine compound.  
   
   
       2 . The organic photosensitive optoelectronic device of  claim 1 , wherein the donor-like material comprises a subphthalocyanine compound.  
   
   
       3 . The organic photosensitive optoelectronic device of  claim 2 , wherein the donor-like material is a boron subphthalocyanine halide.  
   
   
       4 . The organic photosensitive optoelectronic device of  claim 2 , wherein the donor-like material is a boron subphthalocyanine chloride.  
   
   
       5 . The organic photosensitive optoelectronic device of  claim 2 , wherein the subphthalocyanine compound is an oligomer.  
   
   
       6 . The organic photosensitive optoelectronic device of  claim 2 , wherein the subphthalocyanine compound is of the formula  
     
       
         
         
             
             
         
       
     
     wherein R 1  to R 12 , M, and X are each selected independently, at least one of R 1  to R 12  is electron donating or electron withdrawing, and the remaining R 1  to R 12  groups are independently selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro, and any of R 1  to R 12  that are adjacent can be part of a fused aliphatic or aromatic ring, wherein the ring may contain one or more atoms other than carbon, M is boron, a divalent metal, or a trivalent metal, and X is an anionic group.  
   
   
       7 . The organic photosensitive optoelectronic device of  claim 2 , wherein the subphthalocyanine compound is of the formula  
     
       
         
         
             
             
         
       
     
     wherein R 1  to R 12 , M, and X are each selected independently, R 1  to R 12  are independently selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro, and any of R 1  to R 12  that are adjacent can be part of a fused aliphatic or aromatic ring, wherein the ring may contain one or more atoms other than carbon, M is boron, a divalent metal, or a trivalent metal, and X is an anionic group.  
   
   
       8 . The organic photosensitive optoelectronic device of  claim 7 , wherein at least one of R 1  to R 12  is selected from the group consisting of SC 8 H 17 , SC 6 H 5 , SO 2 C 6 H 5 , and SO 2 C 8 H 17 .  
   
   
       9 . The organic photosensitive optoelectronic device of  claim 7 , wherein M is selected from the group consisting of B, Be, Mg, Al, and Ga, and X is selected from the group consisting of halide, alkoxy, phenoxy, hydroxy, aryl, phenyl, and OCOCR 13 R 14 R 15 , wherein R 13 , R 14 , and R 15  are independently selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro.  
   
   
       10 . The organic photosensitive optoelectronic device of  claim 9 , wherein at least one of R 13 , R 14 , and R 15  is selected from the group consisting of SC 8 H 17 , SC 6 H 5 , SO 2 C 6 H 5 , and SO 2 C 8 H 17 .  
   
   
       11 . The organic photosensitive optoelectronic device of  claim 1 , wherein the donor-like material comprises a subporphyrin compound.  
   
   
       12 . The organic photosensitive optoelectronic device of  claim 11 , wherein the subporphyrin compound is of the formula  
     
       
         
         
             
             
         
       
     
     wherein R 1  to R 12 , M, and X are each selected independently, at least one of R 1  to R 12  is electron donating or electron withdrawing, and the remaining R 1  to R 12  are independently selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro, and any of R 1  to R 12  that are adjacent can be part of a fused aliphatic or aromatic ring, wherein the ring may contain one or more atoms other than carbon, M is boron, a divalent metal, or a trivalent metal, X is an anionic group, and Z is N, CH, CR 16 , wherein R 16  is selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro.  
   
   
       13 . The organic photosensitive optoelectronic device of  claim 11 , wherein the subporphyrin compound is of the formula  
     
       
         
         
             
             
         
       
     
     wherein R 1  to R 12 , M, and X are each selected independently, R 1  to R 12  are independently selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro, and any of R 1  to R 12  that are adjacent can be part of a fused aliphatic or aromatic ring, wherein the ring may contain one or more atoms other than carbon, M is boron, a divalent metal, or a trivalent metal, X is an anionic group, and Z is N, CH, CR 16 , wherein R 16  is selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro.  
   
   
       14 . The organic photosensitive optoelectronic device of  claim 13 , wherein M is selected from the group consisting of B, Be, Mg, Al, and Ga, and X is selected from the group consisting of halide, alkoxy, phenoxy, hydroxy, aryl, phenyl, and OCOCR 13 R 14 R 15 , wherein R 13 , R 14 , and R 15  are independently selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro.  
   
   
       15 . The organic photosensitive optoelectronic device of  claim 11 , wherein the subporphyrin compound is an oligomer.  
   
   
       16 . The organic photosensitive optoelectronic device of  claim 1 , wherein the acceptor-like material comprises a subphthalocyanine compound.  
   
   
       17 . The organic photosensitive optoelectronic device of  claim 16 , wherein the acceptor-like material is a boron subphthalocyanine halide.  
   
   
       18 . The organic photosensitive optoelectronic device of  claim 16 , wherein the acceptor-like material is a boron subphthalocyanine chloride.  
   
   
       19 . The organic photosensitive optoelectronic device of  claim 16 , wherein the subphthalocyanine compound is of the formula  
     
       
         
         
             
             
         
       
     
     wherein R 1  to R 12 , M, and X are each selected independently, at least one of R 1  to R 12  is electron donating or electron withdrawing, and the remaining R 1  to R 12  are independently selected from the group consisting of may be electron withdrawing or electron donating, and are preferably independently selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro, and any of R 1  to R 12  that are adjacent can be part of a fused aliphatic or aromatic ring, wherein the ring may contain one or more atoms other than carbon, M is boron, a divalent metal, or a trivalent metal, and X is an anionic group.  
   
   
       20 . The organic photosensitive optoelectronic device of  claim 16 , wherein the subphthalocyanine compound is of the formula  
     
       
         
         
             
             
         
       
     
     wherein R 1  to R 12 , M, and X are each selected independently, R 1  to R 12  are independently selected from the group consisting of may be electron withdrawing or electron donating, and are preferably independently selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro, and any of R 1  to R 12  that are adjacent can be part of a fused aliphatic or aromatic ring, wherein the ring may contain one or more atoms other than carbon, M is boron, a divalent metal, or a trivalent metal, and X is an anionic group.  
   
   
       21 . The organic photosensitive optoelectronic device of  claim 20 , wherein M is selected from the group consisting of B, Be, Mg, Al, and Ga, and X is X is selected from the group consisting of halide, alkoxy, phenoxy, hydroxy, aryl, phenyl, and OCOCR 13 R 14 F 15 , wherein R 13 , R 14 , and R 15  are independently selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro.  
   
   
       22 . The organic photosensitive optoelectronic device of  claim 16 , wherein the subphthalocyanine compound is an oligomer.  
   
   
       23 . The organic photosensitive optoelectronic device of  claim 1 , wherein the acceptor-like material comprises a subporphyrin compound.  
   
   
       24 . The organic photosensitive optoelectronic device of  claim 23 , wherein the subporphyrin compound is of the formula  
     
       
         
         
             
             
         
       
     
     wherein R 1  to R 12 , M, and X are each selected independently, at least one of R 1  to R 12  is electron donating or electron withdrawing, and the remaining R 1  to R 12  are independently selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro, and any of R 1  to R 12  that are adjacent can be part of a fused aliphatic or aromatic ring, wherein the ring may contain one or more atoms other than carbon, M is boron, a divalent metal, or a trivalent metal, X is an anionic group, and Z is N, CH, CR 16 , wherein R 16  is selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro.  
   
   
       25 . The organic photosensitive optoelectronic device of  claim 23 , wherein the subporphyrin compound is of the formula  
     
       
         
         
             
             
         
       
     
     wherein R 1  to R 12 , M, and X are each selected independently, R 1  to R 12  are independently selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro, and any of R 1  to R 12  that are adjacent can be part of a fused aliphatic or aromatic ring, wherein the ring may contain one or more atoms other than carbon, M is boron, a divalent metal, or a trivalent metal, X is an anionic group, and Z is N, CH, CR 16 , wherein R 16  is selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro.  
   
   
       26 . The organic photosensitive optoelectronic device of  claim 23 , wherein the subporphyrin compound is an oligomer.  
   
   
       27 . The organic photosensitive optoelectronic device of  claim 1 , wherein the donor-like material comprises a subporphyrazine compound.  
   
   
       28 . The organic photosensitive optoelectronic device of  claim 27 , wherein the subporphyrazine compound is of formula:  
     
       
         
         
             
             
         
       
     
     wherein R 1  to R 6 , M, X, and Z are each selected independently, at least one of R 1  to R 12  is electron donating or electron withdrawing, and the remaining R 1  to R 6  are selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro, M boron, a divalent metal, or a trivalent metal, and X is an anionic group, and Z is N, CH, CR 16 , wherein R 16  is selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro.  
   
   
       29 . The organic photosensitive optoelectronic device of  claim 27 , wherein the subporphyrazine compound is of formula:  
     
       
         
         
             
             
         
       
     
     wherein R 1  to R 6 , M, X, and Z are each selected independently, R 1  to R 6  are selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro, M boron, a divalent metal, or a trivalent metal, and X is an anionic group, and Z is N, CH, CR 16 , wherein R 16  is selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro.  
   
   
       30 . The organic photosensitive optoelectronic device of  claim 29 , wherein M is selected from the group consisting of B, Be, Mg, Al, and Ga, and X is selected from the group consisting of halide, alkoxy, phenoxy, hydroxy, aryl, phenyl, and OCOCR 13 R 14 R 15 , wherein R 13 , R 14 , and R 15  are independently selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro.  
   
   
       31 . The organic photosensitive optoelectronic device of  claim 1 , wherein the acceptor-like material comprises a subporphyrazine compound.  
   
   
       32 . The organic photosensitive optoelectronic device of  claim 31 , wherein the subporphyrazine compound is of formula:  
     
       
         
         
             
             
         
       
     
     wherein R 1  to R 6 , M, X, and Z are each selected independently, at least one of R 1  to R 12  is electron donating or electron withdrawing, and the remaining R 1  to R 6  are selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro, M boron, a divalent metal, or a trivalent metal, and X is an anionic group, and Z is N, CH, CR 16 , wherein R 16  is selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro.  
   
   
       33 . The organic photosensitive optoelectronic device of  claim 31 , wherein the subporphyrazine compound is of formula:  
     
       
         
         
             
             
         
       
     
     wherein R 1  to R 6 , M, X, and Z are each selected independently, R 1  to R 6  are selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro, M boron, a divalent metal, or a trivalent metal, and X is an anionic group, and Z is N, CH, CR 16 , wherein R 16  is selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro.  
   
   
       34 . The organic photosensitive optoelectronic device of  claim 33 , wherein M is selected from the group consisting of B, Be, Mg, Al, and Ga, and X is selected from the group consisting of halide, alkoxy, phenoxy, hydroxy, aryl, phenyl, and OCOCR 13 R 14 R 15 , wherein R 13 , R 14 , and R 15  are independently selected from the group consisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro.  
   
   
       35 . The organic photosensitive optoelectronic device of  claim 1 , wherein the device is a solar cell, photodetector, or photosensor.  
   
   
       36 . The organic photosensitive optoelectronic device of  claim 1 , wherein the device is a visible spectrum photodetector or photosensor.  
   
   
       37 . The organic photosensitive optoelectronic device of  claim 1 , wherein the heterojunction is a double heterostructure.  
   
   
       38 . The organic photosensitive optoelectronic device of  claim 1 , wherein the heterojunction is a bulk heterojunction.  
   
   
       39 . The organic photosensitive optoelectronic device of  claim 1 , wherein the heterojunction is a planar heterojunction.  
   
   
       40 . A method of preparing a heterojunction, wherein the heterojunction comprises a donor-like material and an acceptor-like material, the method comprising: 
 selecting a donor-like material having a LUMO and a HOMO, selecting a subphthalocyanine or a subporphyrin material, substituted with at least one electron withdrawing or electron donating substituent group, wherein the substituent group modulates the subphthalocyanine or subporphyrin material LUMO and HOMO, such that the subphthalocyanine or subporphyrin material is an acceptor-like material for the donor-like material, and forming a heterojunction from the donor-like and acceptor like materials; or    selecting an acceptor-like material, selecting a subphthalocyanine, subporphyrin, or subporphyrazine material, substituted with at least one electron withdrawing or electron donating substituent group, wherein the substituent group modulates the subphthalocyanine, subporphyrin, or subporphyrazine material LUMO and HOMO, such that the subphthalocyanine, subporphyrin, or subporphyrazine material is a donor-like material for the acceptor-like material, and forming a heterojunction from the donor-like and acceptor like materials.    
   
   
       41 . The organic photosensitive optoelectronic device of  claim 1 , wherein the donor-like material comprises a subphthalocyanine compound, and the acceptor-like material comprises a subphthalocyanine compound.