The availability of purely semiconducting single-walled carbon nanotube (s-SWCNT) dispersions has prompted their widespread application in solution-processed thin-film transistors with excellent device performance but has also raised the question of how their precise composition influences charge transport properties in random networks. Here, we compare hole and electron transport in three different polymer-sorted s-SWCNT networks from nearly monochiral (6,5) nanotubes (diameter 0.76 nm) to mixed networks of s-SWCNTs with medium (0.8–1.3 nm) and large (1.2–1.6 nm) diameters. Temperature-dependent field-effect mobilities are extracted from gated four-point probe measurements that exclude any contributions by contact resistance and indicate thermally activated transport. The mobility data can be fitted to the fluctuation-induced tunneling model, although with significant differences between the network compositions. The network with the broadest diameter and thus bandgap range results in the strongest temperature dependence in agreement with numerical simulations based on a random resistor model of nanotube junctions. However, the experimental data for mixed networks of large diameter nanotubes and their deviation from the simple junction model implies a significant contribution of intra-nanotube transport with its specific diameter and temperature dependence to the overall charge transport properties of the network.

Single‐walled carbon nanotubes (SWNTs) are a promising material for flexible and printed electronics. Efficient dispersion and sorting methods facilitate the production of large quantities of high‐quality semiconducting SWNT inks for direct printing. Here, the suitability of aerosol‐jet printing of polymer‐sorted (6,5) SWNTs for top‐gate field‐effect transistors is investigated. Despite the sonication involved in the printing process, almost no impact on the quality of the SWNTs in terms of defects and length is found. Printed network transistors show reproducible device performance over extended printing periods and for different ink batches with constant printing parameters. Deposition of multiple SWNT layers to obtain thicker and optically dense films increases the effective mobility and on‐conductance, while also decreasing hysteresis. Aerosol‐jet printing of SWNTs is thus suitable for the fabrication of integrated circuits based on nanotube transistors.

Efficient, stable, and solution-based n-doping of semiconducting single-walled carbon nanotubes (SWCNTs) is highly desired for complementary circuits but remains a significant challenge. Here, we present 1,2,4,5-tetrakis(tetramethylguanidino)benzene (ttmgb) as a strong two-electron donor that enables the fabrication of purely n-type SWCNT field-effect transistors (FETs). We apply ttmgb to networks of monochiral, semiconducting (6,5) SWCNTs that show intrinsic ambipolar behavior in bottom-contact/top-gate FETs and obtain unipolar n-type transport with 3-5-fold enhancement of electron mobilities (approximately 10 cm V s), while completely suppressing hole currents, even at high drain voltages. These n-type FETs show excellent on/off current ratios of up to 10, steep subthreshold swings (80-100 mV/dec), and almost no hysteresis. Their excellent device characteristics stem from the reduction of the work function of the gold electrodes via contact doping, blocking of hole injection by ttmgb on the electrode surface, and removal of residual water from the SWCNT network by ttmgb protonation. The ttmgb-treated SWCNT FETs also display excellent environmental stability under bias stress in ambient conditions. Complementary inverters based on n- and p-doped SWCNT FETs exhibit rail-to-rail operation with high gain and low power dissipation. The simple and stable ttmgb molecule thus serves as an example for the larger class of guanidino-functionalized aromatic compounds as promising electron donors for high-performance thin film electronics.

Charge transport in a network of only semiconducting single-walled carbon nanotubes is modeled as a random-resistor network of tube-tube junctions. Solving Kirchhoff's current law with a numerical solver and taking into account the one-dimensional density of states of the nanotubes enables the evaluation of carrier density dependent charge transport properties such as network mobility, local power dissipation, and current distribution. The model allows us to simulate and investigate mixed networks that contain semiconducting nanotubes with different diameters, and thus different band gaps and conduction band edge energies. The obtained results are in good agreement with available experimental data.

The ability to prepare uniform and dense networks of purely semiconducting single-walled carbon nanotubes (SWNTs) has enabled the design of various (opto-)electronic devices, especially field-effect transistors (FETs) with high carrier mobilities. Further optimization of these SWNT networks is desired to surpass established solution-processable semiconductors. The average diameter and diameter distribution of nanotubes in a dense network were found to influence the overall charge carrier mobility; e.g., networks with a broad range of SWNT diameters show inferior transport properties. Here, we investigate charge transport in FETs with nanotube networks comprising polymer-sorted small diameter (6,5) SWNTs (0.76 nm) and large diameter plasma torch SWNTs (1.17−1.55 nm) in defined mixing ratios. All transistors show balanced ambipolar transport with high on/off current ratios and negligible hysteresis. While the range of bandgaps in these networks creates a highly uneven energy landscape for charge carrier hopping, the extracted hole and electron mobilities vary nonlinearly with the network composition from the lowest mobility (15 cm 2 V −1 s −1 ) for only (6,5) SWNT to the highest mobility (30 cm 2 V −1 s −1 ) for only plasma torch SWNTs. A comparison to numerically simulated network mobilities shows that a superposition of thermally activated hopping across SWNT−SWNT junctions and diameter-dependent intratube transport is required to reproduce the experimental data. These results also emphasize the need for monochiral large diameter nanotubes for maximum carrier mobilities in random networks.