- Open Access
Nanomeniscus-induced delivery of liquid solutions for diverse nanofiber fabrication
© An et al.; license Springer. 2015
Received: 19 November 2014
Accepted: 4 February 2015
Published: 1 July 2015
Nanomaterial-delivery fabrication expects high-potential impacts on nanoscience, technology and industry, but still faces limited applicability mainly due to high-field requirement for liquid delivery, complicated intermediate processes, and narrow ink selectivity. Here, we demonstrates a simple, non-template, non-contact and electric field-free fabrication of diverse nanofibers. The process consists of continuous, meniscus-assisted delivery of liquid solutions through a nanoapertured nozzle in ambient conditions, followed by subsequent evaporation of liquid and aggregation of nanoparticle residues. For example, the carbon-nanotube nanofibers of 500 nm diameter exhibit a high shear modulus of ~1.5 GPa and current density up to 104 A/cm2. The results provide a unique, universal and versatile tool with wide selectivity in both ink and substrate.
1 1 Background
Nanomaterial-delivered fabrication [1-7] is a critical step toward realization of molecular architecture/electronics and nano-bio material engineering. Among conventional technologies, it corresponds to the additive nanofabrication method, representing a bottom up approach for nanostructures and nanodevices, which deposits materials onto a substrate. Such additive methods can be classified into two categories: beam-based writing [8,9] and pen-type lithography [10,11]. The direct laser writing is a typical beam-based lithography method and has the advantage of a fast prototyping speed, but it cannot be used to deposit beam-inactive materials. The electron-beam-based and the focused-ion-beam-based lithography allow high-resolution fabrication of various nanomaterials but the required high particle energy and long writing time limit their applications to nanodevice fabrication. On the other hand, the pen-type nanofabrication method such as the dip-pen nanolithography exhibits the advantages of higher throughput and lower energy consumption than the beam-based methods along with previous contributions of nano-dispensing [12-15] and scanning probe lithography methods [16-18]. However, it also suffers from both lack of continuous writing capability and limited ink selectivity. Recently, the meniscus-confined electrodeposition of electrolytes has been developed for fabrication of metallic structures, but its application is restricted to the conducting substrate because it employs the electric field-induced delivery .
Therefore, the low energy consumption, broad selectivity in ink and substrate, and continuous writing capability are still technical challenges for a general realization of the existing additive nanofabrication methods. In other words, one has to overcome the practical limitations of conventional methods in fabrication of diverse nanomaterials; for example, narrow ink/substrate selectivity, complex intermediate processes, difficult individual manipulation of nano-objects, non-applicability of microscale ink-jet printing at the nanoscale, and relatively long manufacturing time. As an alternative approach to address these crucial and demanding issues, we introduce a direct and versatile nanofabrication scheme, which combines the field-free nanomaterial-delivery of liquid solutions (inks) followed by mechanical drawing out of a nanoapertured pipette as well as precise distance controllability and sensitivity of dynamic atomic force microscope (AFM). This method represents substantial advances over current technologies because it demonstrates, (i) realization of general nanofabrication of nanofibers (NFs), (ii) electric field-free, continuous delivery of liquid solutions, (iii) non-template fabrication and in situ characterization of the viscoelastic NFs, (iv) demonstration of wide selectivity in ink (nanoparticles, polymer, ionic/bionic molecules and cabon nano-tube (CNT)) and substrate (mica, glass, gold-coated glass, and graphene) and (v) stable and repeatable operation due to low-energy, non-contact control of the nanoaperture, avoiding its mechanical wear or contact damage.
2 2 Methods
Nanomeniscus-induced delivery of liquid solutions for fabrication of the diverse NFs is realized by using a nanopipette combined with quartz tuning fork (QTF)-based AFM  which was previous nanofluidic and lithographical results. The pulled glass nanopipette, fabricated by a mechanical puller (P-2000, Sutter Instrument Co.), with controlled aperture diameters of ~100 nm and ~500 nm, serves as a nano-nozzle for drawing of low-volume liquid solutions (Additional file 1: Figure S1). When the nanopipette tip, which is a reservoir filled with various liquids such as nanoparticle, CNT, polystyrene solutions, approaches the substrate within ~2 nm, the capillary-condensed water naturally forms in the nanopipette-substrate gap in ambient conditions . This water nanobridge plays a mediating role of a nanoscale liquid channel through which the liquid solution is continuously delivered at any desired locations, even in the absence of applied electric fields once the nanobridge is connected. As the tip retracts at variable speeds, the nanomaterial solutions inside the pipette continue to be pulled out to produces the diverse NFs, consisting of aggregated nanomaterials with the solution itself evaporated in air. Note that the non-contact mode operation of AFM can be achieved due to the high stiffness of the QTF, which produces the well-defined and well-characterized NF preform, while protecting the tip damage and allowing its repetitive and reliable use.
3 3 Results and discussion
3.1 3.1 Characterizations of the fabricated NFs
For investigation of the electrical properties of the NFs, a direct current measurement scheme was implemented on the spot where the NF was fabricated (Additional file 1: Figure S5). After the NF was fabricated on the substrate, the two electrodes were connected with the NF and the electrical current was in situ measured (Figure 2(b)). The NF behaves like a poor conductor (~200 nA at ~1 kV bias potential) compared with the single-crystalline Au nanowire  due to the low dimensional factor, impurity and composition of liquid. Interestingly, several electrical spikes were observed as marked by the arrows, which may be attributed to rearrangement of the nanoparticle clusters within the NF by an applied electric field. Due to the physical similarity between the NF and the molecular architecture based on complex biological materials, the similar current measurement may be useful for such applications as molecular electronics and biomolecule synthesis. We also investigated the optical (or structural) properties of the NFs by analyzing the X-ray diffraction (XRD) patterns and by illuminating the halogen lamp (Figure 2(c)). The test sample for the XRD experiment was prepared by a droplet of the 2 nm Au-particle solution dried on the glass substrate, and the XRD results indicate the presence of the Au (111) states above the SiO2 background. Direct illumination of the halogen lamp on the fabricated Au NF shows the gold-color fluorescence, which confirms the uniformly distributed Au nanoparticles along the NF axis.
3.2 3.2 Wide selectivity in ink and substrate
In particular, the ionic composite NFs could be realized by using deionized (DI) water (with a resistivity of ~18 MΩ · cm) at a low pulling speed of the pipette tip (Additional file 1: Figure S8). In other words, the low-concentration ions in DI-water were well stacked and thus formed the NFs on the boundary rim of the nanoaperture, resulting from fast evaporation of water at a low retraction speed of the tip. In particular, this result is worthy of notice because it suggests one can realize nanomaterial-delivered fabrication even with such a high-purity DI-water. The dye molecule-delivered NFs on the glass and mica substrates were also fabricated and their images were captured by the florescence microscope (FM). In addition, Figure 3(b) shows the OM images (in both transmission and reflection modes) of the fabricated micro ((i), (ii)) as well as nanoscale ((iii), (iv)) Au nanoparticles/NaCl composite fibers. Because the NaCl solution tends to aggregate the Au nanoparticles with each other, the NF drawing experiment had to be performed immediately after the solution is filled in the nanopipette reservoir. Each part of NF having different constituent particles (i.e., Au nanoparticle or NaCl) is distinguished by the contrast of the reflection OM image.
3.3 3.3 Electrical wiring by micro/nanoscale CNT fibers
4 4 Conclusion
We demonstrated a general, non-template, non-contact, and electric field-free nanomaterial-delivery platform for fabrication of diverse NFs in ambient conditions. We showed continuous pulling of flexible NFs, accompanied by in situ mechanical interpretation with a wide selectivity in nanomaterials (inks) and substrates for versatile and direct fabrication. We may further extend our method to fabricate thinner NFs down to 30 nm diameter or to design better characteristic NFs for biology-driven purposes. Our nanoscale fiber-pulling results may also help (i) facilitate in situ fabrication and characterization of the low-dimensional viscoelastic biological materials and (ii) build the nanoscale architectures with various inks for electrical/biological/chemical applications as a candidate to realize the practical field-free nano ink-jet printing or to use as a platform for molecular electronics.
This work was supported by the National Research Foundation of Korea(NRF) grant funded by the Korea government (MSIP) (No. 2009–0083512), Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2013R1A6A3A03063900), and the Brain Korea 21.
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