Investigation of the high electron affinity molecular dopant f6-tcnnq for hole-transport materials

2,2′-(perfluoronaphthalene-2,6-diylidene)dimalononitrile (F6-TCNNQ) is investigated as a molecular p-type dopant in two hole-transport materials, 2,2′,7,7′-tetrakis(N,N-diphenylamino)-9,9-spirobifluorene (Spiro-TAD) and tris(4-carbazoyl-9-ylphenyl)amine (TCTA). The electron affinity of F6-TCNNQ is determined to be 5.60 eV, one of the strongest organic molecular oxidizing agents used to date in organic electronics. p-Doping is found to be effective in Spiro-TAD (ionization energy = 5.46 eV) but not in TCTA (ionization energy = 5.85 eV). Optical absorption measurements demonstrate that charge transfer is the predominant doping mechanism in Spiro-TAD:F6-TCNNQ. The host– dopant interaction also leads to a significant alteration of the host film morphology. Finally, transport measurements done on Spiro-TAD:F6-TCNNQ as a function of dopant concentration and temperature, and using a highly doped contact layer to ensure negligible hole injection barrier, lead to an accurate measurement of the film conductivity and hole-hopping activation energy.