Swagat K. Mohapatra

n-Doping of organic electronic materials using air-stable organometallics.

Air-stable dimers of sandwich compounds including rhodocene and (pentamethylcyclopentadienyl)(arene)ruthenium and iron derivatives can be used for n-doping electron-transport materials with electron affinities as small as 2.8 eV. A p-i-n homojunction diode based on copper phthalocyanine and using rhodocene dimer as n-dopant shows a rectification ratio of greater than 10(6) at 4 V.

Solution doping of organic semiconductors using air-stable n-dopants

Solution-based n-doping of the polymer poly{[N,N′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)} [P(NDI2OD-T2)] and the small molecule 6,13-bis(tri(isopropyl)silylethynyl)pentacene (TIPS-pentacene) is realized with the air-stable dimers of rhodocene, [RhCp2]2, and ruthenium(pentamethylcyclopentdienyl)(1,3,5-triethylbenzene), [Cp*Ru(TEB)]2. Fermi level shifts, measured by direct and inverse photoemission spectroscopy, and orders of magnitude increase in current density and film conductivity point to strong n-doping in both materials. The strong reducing power of these air-stable dopants is demonstrated through the n-doping of TIPS-pentacene, a material with low electron affinity (3.0 eV). Doping-induced reduction of the hopping transport activation energy indicates that the increase in film conductivity is due in part to the filling of deep gap states by carriers released by the dopants.

Production of heavily n- and p-doped CVD graphene with solution-processed redox-active metal–organic species

CVD graphene has been n- and p-doped using redox-active, solution-processed metal–organic complexes. Electrical measurements, photoemission spectroscopies, and Raman spectroscopy were used to characterise the doped films and give insights into the changes. The work function decreased by as much as 1.3 eV with the n-dopant, with contributions from electron transfer and surface dipole, and the conductivity significantly increased.

Passivation of trap states in unpurified and purified C60 and the influence on organic field-effect transistor performance

We investigate trap-state passivation by addition of ultra-low amounts of n-dopants in organic field-effect transistors (OFET) made of as-received and purified fullerene C60. We find a strong dependence of the OFET threshold voltage (VT) on the density of traps present in the layer. In the case of the unpurified material, VT is reduced from 17.9 V to 4.7 V upon trap passivation by a dopant:C60 ratio of ∼10−3, while the Ion/off current ratio remains high. This suggests that ultra-low doping can be used to effectively compensate impurity and defect-related traps.

Reduction of contact resistance by selective contact doping in fullerene n-channel organic field-effect transistors

We have investigated the contact-doping effect on high performance n-channel C60 organic field-effect transistors (OFETs) using the air-stable rhodocene dimer as an n-type dopant. The average charge mobility improved from a value of 0.48 cm2/(Vs) in a reference device to 1.65 cm2/(Vs) for contact-doped devices with a channel length of 25 μm. The operational stability of contact-doped OFETs under continuous stress bias was found similar to the reference devices.

Dopant controlled trap-filling and conductivity enhancement in an electron-transport polymer

Charge transport in organic semiconductors is often inhibited by the presence of tail states that extend into the band gap of a material and act as traps for charge carriers. This work demonstrates the passivation of acceptor tail states by solution processing of ultra-low concentrations of a strongly reducing air-stable organometallic dimer, the pentamethylrhodocene dimer, [RhCp*Cp]2, into the electron transport polymer poly{[N,N′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)}, P(NDI2OD-T2). Variable-temperature current-voltage measurements of n-doped P(NDI2OD-T2) are presented with doping concentration varied through two orders of magnitude. Systematic variation of the doping parameter is shown to lower the activation energy for hopping transport and enhance film conductivity and electron mobility.

Dimers of Nineteen‐Electron Sandwich Compounds: Crystal and Electronic Structures, and Comparison of Reducing Strengths

The dimers of some Group 8 metal cyclopentadienyl/arene complexes and Group 9 metallocenes can be handled in air, yet are strongly reducing, making them useful n-dopants in organic electronics. In this work, the X-ray molecular structures are shown to resemble those of Group 8 metal cyclopentadienyl/pentadienyl or Group 9 metal cyclopentadienyl/diene model compounds. Compared to those of the model compounds, the DFT HOMOs of the dimers are significantly destabilized by interactions between the metal and the central CC σ-bonding orbital, accounting for the facile oxidation of the dimers. The lengths of these CC bonds (X-ray or DFT) do not correlate with DFT dissociation energies, the latter depending strongly on the monomer stabilities. Ru and Ir monomers are more reducing than their Fe and Rh analogues, but the corresponding dimers also exhibit much higher dissociation energies, so the estimated monomer cation/neutral dimer potentials are, with the exception of that of [RhCp2 ]2 , rather similar (-1.97 to -2.15 V vs. FeCp2 (+/0) in THF). The consequences of the variations in bond strength and redox potentials for the reactivity of the dimers are discussed.

Molecular doping and tuning threshold voltage in 6,13-bis(triisopropylsilylethynyl)pentacene/polymer blend transistors

Precise control of the electrical characteristics of organic field-effect transistors is essential for their use in integrated circuits. In addition to the mobility, the threshold voltage, Vth, is a key parameter to control for proper circuit operation. In this work, we demonstrate the controlled tuning of Vth of solution-processed, small-molecule, organic semiconductor transistors via molecular doping of the solution at multiple different doping levels.