Multivalent anions as universal latent electron donors.

Electrodes with low work functions are required to efficiently inject electrons into semiconductor devices. However, when the work function drops below about 4 electronvolts, the electrode suffers oxidation in air, which prevents its fabrication in ambient conditions. Here we show that multivalent anions such as oxalate, carbonate and sulfite can act as powerful latent electron donors when dispersed as small ion clusters in a matrix, while retaining their ability to be processed in solution in ambient conditions. The anions in these clusters can even n-dope the semiconductor core of π-conjugated polyelectrolytes that have low electron affinities, through a ground-state doping mechanism that is further amplified by a hole-sensitized or photosensitized mechanism in the device. A theoretical analysis of donor levels of these anions reveals that they are favourably upshifted from ionic lattices by a decrease in the Coulomb stabilization of small ion clusters, and by irreversibility effects. We attain an ultralow effective work function of 2.4 electronvolts with the polyfluorene core. We realize high-performance, solution-processed, white-light-emitting diodes and organic solar cells using polymer electron injection layers with these universal anion donors, demonstrating a general approach to chemically designed and ambient-processed Ohmic electron contacts for semiconductor devices.

Effects of Planarization of the Triphenylamine Unit on the Electronic and Transport Properties of Triarylamine-Fluorene Copolymers in Both Doped and Undoped Forms.

Triarylamine-alt-fluorene (TAF) copolymers are widely used for hole injection and transport in organic electronics. Despite suggestions to planarize the triphenylamine moiety, little research has been conducted. Here, we report a comprehensive investigation of the effects of planarization on the electronic and transport properties of a model TAF polymer semiconductor core. We compared the conventional twisted-propeller N-4-methoxyphenyl-N,N-diphenylamine-4',4″-diyl (TA) unit and its planarized bridged analogue (bTA) where adjacent o,o'-positions are linked by 1,1-dimethylmethylene. We studied both polyelectrolyte and non-polyelectrolyte forms of this core in both doped and undoped states. We found that planarization leads to an unprecedented trap-free transport of holes, and a pronounced enhancement of their mobility in the undoped state though less so in the doped state. Planarization also induces a slight reduction in the ionization energy of the undoped polymer, consequently lowering the work function of the doped polymer. This is accompanied by small spectral shifts: a red shift in the first absorption band of the undoped polymer and a blue shift in the first absorption band of the polaron. Furthermore, this study unveils new fundamental features of TAF polymers: (i) Doping induces the formation of three polaron bands within the subgap. (ii) Absorption of both neutral and polaron segments exhibit a linear intensity relationship with doping level. (iii) Electrical conductivity reaches a maximum at the half-doped state, varying as σ ∼ (x (1 - x))3 for 0.1 ≲ x ≲ 0.9, where x is the doping level. Finally, we demonstrate the successful integration of these self-compensated hole-doped TAF polymers as efficient hole injection layers in organic semiconductor diodes.

Overcoming the water oxidative limit for ultra-high-workfunction hole-doped polymers.

It is widely thought that the water-oxidation reaction limits the maximum work function to about 5.25 eV for hole-doped semiconductors exposed to the ambient, constrained by the oxidation potential of air-saturated water. Here, we show that polymer organic semiconductors, when hole-doped, can show work functions up to 5.9 eV, and yet remain stable in the ambient. We further show that de-doping of the polymer is not determined by the oxidation of bulk water, as previously thought, due to its general absence, but by the counter-balancing anion and its ubiquitously hydrated complexes. The effective donor levels of these species, representing the edge of the 'chemical' density of states, can be depressed to about 6.0 eV below vacuum level. This can be achieved by raising the oxidation potential for hydronium generation, using large super-acid anions that are themselves also stable against oxidation. In this way, we demonstrate that poly(fluorene-alt-triarylamine) derivatives with tethered perfluoroalkyl-sulfonylimidosulfonyl anions can provide ambient solution-processability directly in the ultrahigh-workfunction hole-doped state to give films with good thermal stability. These results lay the path for design of soft materials for battery, bio-electronic and thermoelectric applications.