The search for low‐cost, large‐area, flexible devices has led to a remarkable increase in the research and development of organic semiconductors, which serve as one of the most important components for organic field‐effect transistors (OFETs). In the current review, we highlight deposition techniques that offer precise control over the location or in‐plane orientation of organic semiconductors. We focus on various vapor‐ and solution‐processing techniques for patterning organic single crystals in desired locations. Furthermore, the alignment of organic semiconductors via different methods relying on mechanical forces, alignment layers, epitaxial growth, and external magnetic and electric fields are surveyed. The advantages, limitations, and applications of these techniques in OFETs are also discussed.

Various methods for the patterned assembly of metal nanoparticles have been developed in order to harness their unique electrical and optical properties for device applications. This paper discusses a method for direct writing of Au nanoparticles at nanoscale resolution using dip-pen nanolithography. First, a procedure was developed for increasing the loading of Au nanoparticles onto AFM tips to prolong patterning life. AFM tips were subsequently imaged by scanning electron microscopy to determine ink coverage and to gain insight into the deposition process. Next, surface interactions, relative humidity, and writing speed were controlled to determine an optimal range of conditions for deposition. Various ink-substrate combinations were studied to elucidate the dependence of deposition on interactions between Au nanoparticles and the substrate surface; inks consisted of positively and negatively charged particles, and substrates were SiO(2) surfaces modified as hydrophilic or hydrophobic and interacted electrostatically or covalently with Au nanoparticles. Results indicate that a highly hydrophilic surface is required for Au nanoparticle deposition, unless covalent binding can occur between the Au and substrate surface. The optimal range of relative humidity for patterning was found to be 40-60%, and Au nanoparticle deposition was not sensitive to writing speeds ranging from 0.01 to 2 microm/s.

Two efficient approaches to assembling organic semiconducting single crystals are described. The methods rely on solvent wetting and dewetting on substrates with patterned wettability to selectively direct the deposition or removal of organic crystals. Substrates were functionalized with different self-assembled monolayers (SAMs) to achieve the desired wettabilities. The assembly of different organic crystals over centimeter-squared areas on Au, SiO2, and flexible plastic substrates was demonstrated. By designing line features on the substrate, the alignment of crystals, such as CuPc needles, was also achieved. As a demonstration of the potential application of this assembly approach, arrays of single-crystal organic field-effect transistors were fabricated by patterning organic single crystals directly onto and between transistor source and drain electrodes.

This paper discusses a method for the direct patterning of Au electrodes at nanoscale resolution using dip-pen nanolithography, with proof-of-concept demonstrated by creating single-walled carbon nanotube devices. This technique enables insight into three key concepts at the nanoscale: using dip-pen nanolithography as an alternative to electron-beam lithography for writing contacts to carbon nanotubes, understanding the integrity of contacts and devices patterned with this technique, and on a more fundamental level, providing a facile method to compare and understand electrical and Raman spectroscopy data from the same isolated carbon nanotube. Electrical contacts to individual and small bundle single-walled carbon nanotubes were masked by an alkylthiol that was deposited via dip-pen nanolithography on a thin film of Au evaporated onto spin-cast, nonpercolating, and highly isolated single-walled carbon nanotubes. A wet Au etching step was used to form the individual devices. The electrical characteristics for three different single-walled carbon nanotube devices are reported: semimetallic, semiconducting, and metallic. Raman analysis on representative devices corroborates the results from AFM imaging and electrical testing. This work demonstrates a technique for making electrical contact to nanostructures of interest and provides a platform for directly corroborating electrical and optical measurements. The merits of using dip-pen nanolithography include flexible device configuration (such as varying the channel length and the number, size, and orientation of contacts), targeted patterning of individual devices with imaging and writing conducted in the same instrument under ambient conditions, and negligible damage to single-walled carbon nanotubes during the fabrication process.

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