The discovery of air-stable n-dopants for organic semiconductor materials has been hindered by the necessity of high-energy HOMOs and the air sensitivity of compounds that satisfy this requirement. One strategy for circumventing this problem is to utilize stable precursor molecules that form the active doping complex in situ during the doping process or in a postdeposition thermal- or photo-activation step. Some of us have reported on the use of 1H-benzimidazole (DMBI) and benzimidazolium (DMBI-I) salts as solution- and vacuum-processable n-type dopant precursors, respectively. It was initially suggested that DMBI dopants function as single-electron radical donors wherein the active doping species, the imidazoline radical, is generated in a postdeposition thermal annealing step. Herein we report the results of extensive mechanistic studies on DMBI-doped fullerenes, the results of which suggest a more complicated doping mechanism is operative. Specifically, a reaction between the dopant and host that begins with either hydride or hydrogen atom transfer and which ultimately leads to the formation of host radical anions is responsible for the doping effect. The results of this research will be useful for identifying applications of current organic n-doping technology and will drive the design of next-generation n-type dopants that are air stable and capable of doping low-electron-affinity host materials in organic devices.

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Tuning the threshold voltage of a transistor is crucial for realizing robust digital circuits. For silicon transistors, the threshold voltage can be accurately controlled by doping. However, it remains challenging to tune the threshold voltage of single-wall nanotube (SWNT) thin-film transistors. Here, we report a facile method to controllably n-dope SWNTs using 1H-benzoimidazole derivatives processed via either solution coating or vacuum deposition. The threshold voltages of our polythiophene-sorted SWNT thin-film transistors can be tuned accurately and continuously over a wide range. Photoelectron spectroscopy measurements confirmed that the SWNT Fermi level shifted to the conduction band edge with increasing doping concentration. Using this doping approach, we proceeded to fabricate SWNT complementary inverters by inkjet printing of the dopants. We observed an unprecedented noise margin of 28 V at V DD = 80 V (70% of 1/2V DD ) and a gain of 85. Additionally, robust SWNT complementary metal−oxide−semiconductor inverter (noise margin 72% of 1/2V DD ) and logic gates with rail-torail output voltage swing and subnanowatt power consumption were fabricated onto a highly flexible substrate. nanomaterials | n-doping | inkjet-printed | CMOS circuit F lexible electronics have attracted increasing attention recently due to the plethora of possible and realized applications in radio-frequency identification cards (1, 2), flexible displays (3, 4), and digital processors (5). Solution-processed single-walled carbon nanotubes (SWNTs) are a promising candidate for flexible circuits due to their high charge carrier mobility (6), excellent flexibility/stretchability (7-9), and their compatibility with lowcost, large-area manufacturing processes, such as printing (1, 10) of SWNTs. Their applications in thin-film transistors (TFTs) and integrated logic circuits (11-14) have been demonstrated. However, to achieve robust digital circuits with high immunity against the influence of electronic noise in the system, it is important to be able to control the specific value of the threshold voltage of a transistor during the fabrication process (15,16). This is because transistor threshold voltage determines the input voltage at which a circuit switches between two logic states (trip voltage of an inverter). When the trip voltage is half of the supply voltage, the circuit has the largest noise margin, which is a quantitative measure of the immunity of a logic circuit against noise and a figure of merit to characterize the robustness of the circuit (17, 18). If threshold voltage cannot be controlled during the fabrication process, the resulting circuit might not work reliably due to the electrical noise that is always present in the system. Because SWNTs have ambipolar electrical transport properties (19), accurately tuning the threshold voltage permits the construction of complementary metal−oxide−semiconductor (CMOS) circuits that use both the p-type and n-type character of SWNTs. The advantages of CMOS circuits compared with unipolar ...

Controlling the Dirac point of graphene is essential for complementary circuits. Here, we describe the use of 2-(2-methoxyphenyl)-1,3-dimethyl-2,3-dihydro-1H-benzoimidazole (o-MeO-DMBI) as a strong n-type dopant for chemical-vapor-deposition (CVD) grown graphene. The Dirac point of graphene can be tuned significantly by spin-coating o-MeO-DMBI solutions on the graphene sheets at different concentrations. The transport of graphene can be changed from p-type to ambipolar and finally n-type. The electron transfer between o-MeO-DMBI and graphene was additionally confirmed by Raman imaging and photoemission spectroscopy (PES) measurements. Finally, we fabricated a complementary inverter via inkjet printing patterning of o-MeO-DMBI solutions on graphene to demonstrate the potential of o-MeO-DMBI n-type doping on graphene for future applications in electrical devices.