Controlled growth of metal–organic frameworks (MOFs) nanocrystals on requisite surfaces is highly desired for myriad applications related to catalysis, energy, and electronics. Here, this challenge is addressed by overlaying arbitrary surfaces with a thermally evaporated metal layer to enable the well‐aligned growth of ultralong quasi‐2D MOF nanoarrays comprising cobalt ions and thiophenedicarboxylate acids. This interfacial engineering approach allows preferred chelation of carboxyl groups in the ligands with the metal interlayers, thereby making possible the fabrication and patterning of MOF nanoarrays on substrates of any materials or morphologies. The MOF nanoarrays grown on porous metal scaffolds demonstrate high electrocatalytic capability for water oxidation, exhibiting a small overpotential of 270 mV at 10 mA cm−2, or 317 mV at 50 mA cm−2 as well as negligible decay of performance within 30 h. The enhanced performance stems from the improved electron and ion transport in the hierarchical porous nanoarrays consisting of in situ formed oxyhydroxide nanosheets in the electrochemical processes. This approach for mediating the growth of MOF nanoarrays can serve as a promising platform for diverse applications.
Coordination polymers (CPs) are a class of crystalline solids that are considered brittle, due to the dominance of directional coordination bonding, which limits their utility in flexible electronics and wearable devices. Hence, engineering plasticity into functional CPs is of great importance. Here, we report plastic bending of a semiconducting CP crystal, Cu-Trz (Trz = 1,2,3-triazolate), that originates from delamination facilitated by the discrete bonding interactions along different crystallographic directions in the lattice. The coexistence of strong coordination bonds and weak supramolecular interactions, together with the unique molecular packing, are the structural features that enable the mechanical flexibility and anisotropic response. The spatially resolved analysis of short-range molecular forces reveals that the strong coordination bonds, and the adaptive C–H···π and Cu···Cu interactions, synergistically lead to the delamination of the local structures and consequently the associated mechanical bending. The proposed delamination mechanism offers a versatile tool for designing the plasticity of CPs and other molecular crystals.
Most electronics consist of functional thin films with tens of nanometer thicknesses. It is usually challenging to control the growth of these thin films using conventional solution‐based approaches. Nanoadditive manufacturing, a method to deposit electronically desired molecules, polymers, or nanomaterials in a layer‐by‐layer (LbL) fashion, has emerged as a promising technique for the precise control of film growth and device fabrication. Here, basic principles of nanoadditive manufacturing approaches with self‐limiting characteristics are summarized with a particular focus on Langmuir–Blodgett assembly and LbL assembly. Additively manufactured electronic thin films with properties of conductors, semiconductors, and dielectrics are reviewed, followed by a discussion of their application in various electronics, such as field‐effect transistors, sensors, memory devices, photodetectors, light‐emitting diodes, and electrochromic devices. Finally, challenges and future developments of these approaches are proposed. The resulting analysis reveals promising opportunities of nanoadditive manufacturing for the solution‐based fabrication of electronic devices.
Stretchable conductors capable of precise micropatterning are imperative for applications in various wearable technologies. Metallic nanoparticles with low aspect ratios and miniscule sizes are preferred over metallic nanowires or nanoflakes for such applications. However, nanoparticles tend to lose mutual contact during stretching. Therefore, they are rarely used alone in stretchable conductors. In this study, electronic inks comprising silver nanoparticles (AgNPs) for the high‐resolution printing of stretchable conductors are reported. AgNPs are synthesized using aqueous polyurethane micelles, which are subsequently disentangled into polymeric chains in isopropanol to stabilize the inks. The ink rheology can be arbitrarily tuned to allow direct‐write printing with a minimum feature width of 3 µm. Owing to the absence of extra surfactants, direct drying of such inks at room temperature provides the stretchable conductors with an initial conductivity of 8846 S cm−1 and conductivity of 1305 S cm−1 at 100% strain. This enhanced performance is attributed to the conductive percolations through assemblies of AgNPs adapting to the strain and is equivalent to those of stretchable conductors filled with Ag nanowires or flakes. These inks are promising for the scalable fabrication of highly integrated stretchable electronics.
Understanding the effect of short channels on the performance of fieldeffect transistors (FETs) from emerging low-dimensional semiconductors is crucial to estimate their suitability in high-density integrated circuits. To this end, intricate and costly equipment capable of nanoscale photolithography or e-beam lithography is usually required to fabricate FETs with shrinking channel lengths. Here, the authors propose an economical suspended nanofiber lithography technique with short-channel processing capability, and compatibility with modern semiconductor foundries. By combining the merits of the near-field electrohydrodynamic printing of nanofibers and microscale photolithographic process, the authors successfully fabricate short channels with lengths as small as 48 nm via masks of suspended nanofibers, whose diameters are easily tuned by adjusting the printing conditions. This technique is further applied for exploring the performance of short-channel FETs using semiconductors such as single-walled carbon nanotubes or electrochemically-exfoliated MoS 2 . Their performance is comparable to those made from more demanding lithography methods. This economical nanofabrication technique is promising to be applied on a variety of semiconductors for highly integrated fabrication of submicron short-channel device arrays.
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