High work function transparent conductors

Abstract

There is provided a transparent conductor including conductive nanoparticles and at least one of (a) a fluorinated acid polymer and (b) a semiconductive polymer doped with a fluorinated acid polymer. The nanoparticles are carbon nanoparticles, metal nanoparticles, or combinations thereof. The carbon and metal nanoparticles are selected from nanotubes, fullerenes, and nanofibers. The acid polymers are fluorinated or highly fluorinated and have acidic groups including carboxylic acid groups, sulfonic acid groups, sulfonimide groups, phosphoric acid groups, phosphonic acid groups, and combinations thereof. The semiconductive polymers comprise homopolymers and copolymers derived from monomers selected from substituted and unsubstituted thiophenes, pyrroles, anilines, and cyclic heteroaromatics, and combinations of those. The compositions may be used in organic electronic devices (OLEDs).

1 . A transparent conductor having a work function greater than 4.7 eV comprising conductive nanoparticles, a fluorinated acid polymer, and a semiconductive polymer doped with a fluorinated acid polymer. 
     
     
         2 . A transparent conductor of  claim 1  wherein the nanoparticles are selected from carbon and metal nanoparticles and combinations thereof. 
     
     
         3 . A transparent conductor of  claim 2  wherein the nanoparticles are selected from nanotubes, fullerenes, and nanofibers, and combinations thereof. 
     
     
         4 . A transparent conductor of  claim 1  wherein each semiconductive polymer comprises one or more independently substituted or unsubstituted thiophene monomers. 
     
     
         5 . A transparent conductor of  claim 4  wherein the thiophene monomers have structure represented by formulas selected from Formula I and Formula Ia: 
       
         
           
           
               
               
           
         
         wherein:
 R 1  is independently selected so as to be the same or different at each occurrence and is selected from hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ester sulfonate, and urethane; or both R 1  groups together may form an alkylene or alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic or alicyclic ring, which ring may optionally include one or more divalent nitrogen, sulfur or oxygen atoms; and 
 
       
       
         
           
           
               
               
           
         
         wherein: 
         R 7  is the same or different at each occurrence and is selected from hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane, with the proviso that at least one R 7  is not hydrogen, and 
         m is 2 or 3. 
       
     
     
         6 . A transparent conductor of  claim 1  wherein the fluorinated acid polymer has a backbone selected from polyolefins, polyacrylates, polymethacrylates, polyimides, polyamides, polyaramids, polyacrylamides, polystyrenes, and copolymers thereof. 
     
     
         7 . A transparent conductor of  claim 6  wherein the fluorinated acid polymer backbone is fluorinated. 
     
     
         8 . A transparent conductor of  claim 7  wherein the fluorinated acid polymer has fluorinated pendant groups selected from ether sulfonates, ester sulfonates, and ether sulfonimides. 
     
     
         9 . A transparent conductor of  claim 6  wherein the fluorinated acid polymer comprises one or more independently substituted or unsubstituted monomers selected from styrene sulfonic acids or sulfonated ether sulfones, trifluorostyrene sulfonates, sulfonimides, perfluoroalkyl sulfonate ethers, fused polycyclic fluoronated acids, and perfluoroalkyl sulfonic acid ethers. 
     
     
         10 . A transparent conductor of  claim 9  wherein the perfluoroalkyl sulfonate ethers have a structure represented by Formula XI: 
       
         
           
           
               
               
           
         
         where: 
         R 16  is a fluorinated alkyl or a fluorinated aryl group; 
         a, b, c, d, and e are each independently 0 or an integer from 1 to 4; and 
         n is at least 4. 
       
     
     
         11 . A transparent conductor of  claim 1  wherein the fluorinated acid polymer comprises polymeric acids comprising functional groups selected from carboxylic, sulfonic, phosphoric, and phosphonic acid groups and sulfonimides, including combinations thereof. 
     
     
         12 . A transparent conductor of  claim 11  wherein the functional groups are present on the polymeric backbone, side chains, pendant groups, or combinations thereof. 
     
     
         13 . A transparent conductor of  claim 12  wherein the pendant groups comprise siloxane sulfonic acid. 
     
     
         14 . A transparent conductor of  claim 12  wherein the pendant groups comprise groups selected from structures represented by Formula XIV and Formula XV. 
     
     
         15 . A transparent conductor of  claim 11  wherein the fluorinated acid polymer is a colloid-forming polymeric acid. 
     
     
         16 . A transparent conductor of  claim 15  wherein the fluorinated acid polymer comprises an FSA polymer. 
     
     
         17 . A transparent conductor of  claim 1  further comprising a second polymer comprising one or more independently substituted or unsubstituted monomers selected from alkenyls, alkynyls, arylenes, and heteroarylenes. 
     
     
         18 . A transparent conductor having a work function greater than 4.7 eV comprising a fluorinated acid polymer, a semiconductive polymer doped with a fluorinated acid polymer, and a second polymer, the second polymer comprising one or more independently substituted or unsubstituted monomers selected from alkenyls, alkynyls, arylenes, and heteroarylenes. 
     
     
         19 . An electronic device comprising a transparent conductor of  claim 1 . 
     
     
         20 . An electronic device of claim  30  comprising an anode layer, wherein the anode layer comprises the transparent conductor. 
     
     
         21 . An electronic device comprising a transparent conductor of  claim 18 . 
     
     
         22 . An electronic device of  claim 21  comprising an anode layer, wherein the anode layer comprises the transparent conductor.