Fabrication of nanoribbons by dielectrophoresis assisted cold welding of gold nanoparticles on mica substrate

Using alternating current electric fields, nanoribbons are fabricated from an aqueous suspension of gold nanoparticles (AuNPs) on mica substrate without resorting to further chemical functionalization of AuNPs. The potential and kinetic energies of AuNPs subjected to attractive forces from a mica substrate provide sufficient energy to pass the diffusion barrier of the gold atoms, which eventually leads to cold welding. A dielectrophoresis force exerted on polarizable particles in a non-uniform electric field contributes to the directed growth of the cold welding that occurs by adjusting the lattice structures of AuNPs. Depending on the concentration of the AuNP suspension, the frequency of the electric field, and the geometry of electrodes, various morphologies of nanoribbons are fabricated. It turns out that the welded region is nearly perfect to provide the same crystal orientation and strength as the rest of the nanostructures, which can be extensively utilized in the fabrication of various nanostructures.

cold welding can occur easily on a substrate since there are so-called 'self-adjustment' that matches crystalline orientations, requiring little external forces. Thus, the idea of cold-welding has become an attractive process as an efficient assembly tool for nanostructures without any loss of original characteristics. Generally, the high quality in the cold welding of suspended AuNPs on mica substrate is attributed to the following ingredients: 'oriented-attachment' naturally activated in the AuNP suspension on mica substrate, 'enhanced atomic diffusion' from the high surface to volume ratio of AuNPs, and 'surface relaxation and reconstruction' 16 . No systematic studies, however, have been conducted in combination with cold welding of the AuNPs during the DEP process. However, ready-made AuNPs include a high concentration of stabilizers to prevent the aggregation of AuNPs by any disturbances, which in turn makes the cold-welding difficult. In this paper, through green synthesis 18 followed by the removal of stabilizers, cold-welding successfully occurs on mica substrate, which can be extensively used for the fabrication tool of elemental nanostructures. Without resorting to further chemical functionalization of AuNPs or substrates, we use the DEP forces for the directed fabrication of various nanostructures from the AuNPs in liquid suspensions where stabilizers are removed after the green synthesis. Depending on the concentration of AuNP suspension, the frequency and strength of electric field, and electrode geometry, various nanostructures can be fabricated between the electrodes. It has an immense potential for utilization in the field of nanotechnology. We discuss about DEP-assisted cold welding of AuNPs on mica substrate through the observation of High Resolution -Transmission Electron Microscope (HR-TEM), AFM, and Field Emission -Scattering Electron Microscope (FE-SEM) images. The DEP-assisted cold welding is simulated using LAMMPS 19 (Large-scale Atomic/Molecular Massively Parallel Simulator) molecular dynamics (MD) computations.

Results and Discussions
Cold welding of AuNps. Figure 1(a,b) show the HR-TEM images of AuNPs synthesized using green tea extract as a reducing agent (Green synthesis 18 ). We noticed that the size of the AuNPs measured by the HR-TEM images was smaller than 20 nm as shown in Fig. 1(b,c).
When measuring the size of the AuNPs, we observed a significant difference; the size of the AuNPs in the AFM image (20~40 nm) is much larger than those in the HR-TEM image (~20 nm) as shown in Fig. 1(c,f), due to the cold welding phenomenon. It is well known that there is a strong attractive force between Au atoms and silicate in mica substrate 15 . Due to the attractive forces from the mica substrate, sphere-shaped AuNPs grow only on the plane parallel to the mica substrate. Compared to nanowires and nanofilms, the AuNPs in the suspension are able to freely rotate so that the cold welding goes along to adjust the lattice structure of the AuNPs.
Dep-assisted cold welding. If the aqueous suspension of AuNPs on mica substrate is subjected to an electric field, the cold welding with DEP forces lead to various shapes of nanostructures as shown in Fig. 1(g,h). The phase image (h) confirms that the grown structures were made of gold. In the FE-SEM image (i), a nanoribbon grew between the AuNPs where the concentration of the AuNPs was appropriate (See right upper inset in (i)). For the DEP, a function generator is operated at a frequency between 100 Hz and 10 MHz and a peak-to-peak voltage V pp of 1-10 V, as shown in Fig. 2(a).
Nanoribbon chaining occurs such that AC field generates a DEP force exerted on the AuNPs adjacent to the electrodes and a dipole-dipole interaction between AuNPs far from the electrodes. The suspended AuNPs on mica substrate in an electric field are subjected to the following forces; ① F DEP (DEP force), ② F mica (Lennard-Jones potential force from mica substrate), ③ F Coulomb (Coulomb force between charged atoms), and F Lorentz (Lorentz force in electric field) in Fig. 2 πε ω = ∇ is proportional to particle volume a 3 and the gradient of electric field squared E rms . ε m , E rms , and ω are the permittivity of the suspending medium, the root-mean-squared value and angular frequency of electrical field, respectively. Re[K(ω)] is the real part of the Clausius-Mossotti factor. The DEP force does not contribute to the aggregation of AuNPs but accumulates the AuNPs near the tip of the nanostructure to sustain its growth. F Lotentz is eliminated since the overall charge of each AuNP equals zero. F Coulomb attracts AuNPs for chaining and F mica induces the cold welding, after which the grown AuNPs are subjected to a repulsive force ④ F Coulomb perpendicular to the DEP force (Refer to Supplement: Movie 1).
In the HR-TEM images of Fig. 3(a-c), the sample was obtained by placing a HR-TEM grid on mica substrate subjected to AC electric field. The frequency and strength of AC electric field were 100 kHz and 5 V, respectively. The electric field strength and AuNP concentration are of major importance because they must exceed a threshold value for the nanoribbons to start growing. Since the gap of the electrodes is larger than 100 μm, the aggregated AuNPs play the role of conductive objects as shown in (d).
parametric study. When subjected to an electric field, an AuNP has polarity due to the distribution of induced charge. The dipole-dipole attraction of AuNPs does not occur when the concentration of the AuNPs is too low. If the concentration of the AuNPs is too high, the AuNPs simply grow in a radial direction rather than forming nanoribbons as shown in Fig. 4(d,g).
The exerted DEP force makes the grown AuNPs gather but fails to form a continuous nanoribbon due to the large size of the AuNPs. The 'pearl-chain formation' is associated with the induced dipole-dipole interaction between AuNPs that are brought together by the DEP forces. With a twice-diluted suspension, a long nanoribbon is grown between the aggregated AuNPs in (e, h). The AuNPs gather on the surface of the electrode where a big gradient of electric field is observed, which induces the growth of a nanoribbon and then the increase of the gradient of electric field as well. The gradient of electric field enforces the AuNPs to move in the direction of the electric field. This DEP transport increases the density of the AuNPs and eventually induces a polarity-polarity attraction between AuNPs. Chaining of AuNPs is conducted by the Lorentz and Coulombic forces from the distribution of surface charge in the AuNPs. The threshold effect of the AuNP concentration implies that aggregation occurs only when the concentration of AuNPs accumulated near the tip of nanoribbon is sufficiently high to sustain the Figure 1. Characterization of morphology for synthesized AuNPs: All AuNPs in the images were synthesized with HAuCl 4 •3H 2 O as a precursor ion. The reducing agent was a green tea extract. Green synthesis: 75 AuNPs from a randomly selected area in a HR-TEM image (a) were used to measure the average diameter. Size histogram in (c) shows an average size of 8.7 ± 1.77 nm. Cold welding on mica substrate: 75 AuNPs from a randomly selected area in amplitude error image in (d) were used to measure the average diameter. Size histogram in (F) shows an average size of 37.3 ± 9.3 nm. DEP-assisted cold welding: AC electric potential of 1 V and the frequency of 100 Hz were used in the amplitude error (g) and the phase (h) images of AuNPs. In the FE-SEM image (i) nanoribbons grew between AuNPs where the concentration of AuNPs was appropriate (See right upper inset). If the concentration was high, the AuNPs simply grew their diameters (See left lower inset). www.nature.com/scientificreports www.nature.com/scientificreports/ growth of nanoribbon and prevent depletion effects at the tips. In the phase image (h), we observe thin nanoleaves forming from ultra-small AuNPs, where the highest field gradients are required and found near the conductive objects. Due to Coulomb forces, if the neighboring nanoribbons are close enough, polarized nanoribbons attract the neighboring ones to form strands parallel to their long axes. A nanoleaf is formed from the cold welding of nanoribbon strands. For a 5-times diluted suspension, no more nanoleaves are found as shown in (f, i).

Effect of frequency.
We investigate the characteristics of nanoribbons by varying the frequency of exerted electric field. In Fig. 5, most of the nanoribbons are generally aligned perpendicular to the electrodes while slightly deviated ones are present due to conductive objects. Further increase of frequency yields nanoribbons with no directivity in Fig. 5(e,f). By increasing the frequency, the long, thick, and winding nanoribbons are turned into short, thin, and straight ones in Fig. 5. Depending on the size of the synthesized AuNPs, 1.6~4.7 nm high (g), 11~28 nm wide (h), and 0.4~1 μm long nanoribbons are constructed.
Effect of electrode geometry. The strength of the electric field does not significantly affect the aggregation but contributes in the aligning of the AuNPs. Thus, a small electric potential of 1 V pp is applied to prevent possible thermal effects. Also, the AuNP suspension was pipetted onto the top of the mica substrate whereas the electrodes were attached on the bottom. The direction of nanoribbon growth is controlled by disturbing the homogeneity of electric field, which is naturally done by forming conductive objects in the gap between the electrodes. Such www.nature.com/scientificreports www.nature.com/scientificreports/ objects create a gradient in the electric field and cause the nanoribbon to grow toward them. For the controlled applications of DEP, a non-uniform electric field established by electrode geometry is necessary.
Since the DEP force is proportional to the gradient of electric field squared, we investigate the effect of electrode geometry on ∇E rms 2 . To obtain a qualitative distribution of ∇E , rms 2 mica, electrodes, and water are modeled by a multi-physics analysis code, COMSOL. Figure 6 shows the mathematical models of the mica (a) and the water (b). The electrodes are attached on the bottom surface of mica to avoid direct contact with water. Figure 6(c) shows the streamline of the obtained electric field vector when the peak to peak voltage of V pp = 10 is applied.
Electrostatic analysis is carried out to investigate the effect of electrode geometry on the electric field in the space of water. In 2-dimensional cases, the parallel electrodes produce no electric field along the vertical centerline of electrode gap in Fig. 6(d). By varying the inclined angle of the electrode to the vertical centerline, various electric fields are observed in Fig. 6(e) for 30°, (f) for 45°, and (g) for 60°. At the midpoint between the tips of the electrodes, the 45° inclined electrodes produce the strongest electric field. For the 3-dimensional cases, top views are shown in Fig. 6(h-k). The distributions of the electric field are similar to the 2-dimensional cases except the addition of a downward (from top to bottom) electric field. At the midpoint, the 45° inclined electrodes in Fig. 6(j) also produce the strongest electric field with more complicated distribution due to the downward one. For the parallel case, the electric field disappears along the centerline and thus only cold welding occurs due to the www.nature.com/scientificreports www.nature.com/scientificreports/ weak DEP force as shown in Fig. 7(a,b). Among the inclined cases, the 45° inclined one showed the best performance and produced many nanostructures due to sufficient DEP force in (c) and (d).
MD simulation of Dep-assisted cold welding. The MD method and the numerical model for the mica substrate are constructed, based on ref. 16 . We consider the electrical interactions as well as the van der Waals force, which is a short range force between the atoms in Au and mica. However, the electrostatic force, a long range force, is induced by charges due to electric field and can attract atoms located far away. Induced charge distribution is considered on the surface of the AuNPs. Since the charged surface atoms are subjected to additional forces like Lorentz and Coulomb forces, the motion of AuNPs is affected by an external electric field (Refer to Supplement: Movie 1). To observe the phenomenon that AuNPs are affected by the external electric field, we performed LAMMPS 19 simulation for 7 AuNPs as shown in Fig. 8a. Each AuNP is composed of 959 Au atoms and all AuNPs are attached on Muscovite mica substrate. The total number of atoms is 49,721. The interatomic potential employed to consider interaction between Au-Au atoms in the simulations is described by the embedded atom method (EAM) 20 where the potential is described by a pair potential and a function of the electronic density. www.nature.com/scientificreports www.nature.com/scientificreports/ Simulations are performed such that all atoms maintain an isothermal state of 358 K under x-directional electric field,  = . E V 0 05 ( /A). The contour in an AuNP indicates the magnitude of charge. Without an electric field, the particles are not aggregated (a-2, a-3) since they are located far away. Figure 8(b) shows the result of simulation, where the AuNPs are aligned in the direction of the electric field. The atoms parallel to the direction of the electric field are charged with opposite polarity and attract each other (b-2). However, the aggregated particles perpendicular to the electric field direction are charged with same polarity, which results in a repulsive force (b-3). The AuNPs grow in the plane parallel to the mica substrate, maintaining regular lattice structures. The welded AuNPs retain their crystalline fcc structure even in the welded region, in agreement with the known experimental findings 14 that the few defects introduced in the process reconstruct to restore the fcc structure. In the cold welding process, the AuNPs go through an iterative process of clustering and migrating until they are sufficiently stabilized.
To measure the quality of lattice structures, we consider the history of centro-symmetry parameter during the cold welding. The centro-symmetry parameter 21 in Fig. 8(c) is used to identify defects in crystals such as stacking faults in fcc (face-centered cubic) structures. The stacking faults expand from the welding surface as cold welding progresses. The contour in an AuNP indicates the magnitude of stacking faults. After some relaxation period, the regular fcc structure is quickly recovered (Refer to Supplement: Movie 2). The centro-symmetry analysis shows that the cold welding occurred with low stress, and at the end of the process, a crystalline structure with very few defects was achieved, recovering most of original characteristics of the pristine AuNPs. Figure 9 shows the surface of an AuNP consisting of {111} and {100} planes.
The AuNPs rotate in the same direction since the unbalance forces from mica substrate are much bigger that those from Coulomb forces arising from the lattice mismatch of two AuNPs. Just before the cold welding, all the AuNPs are aligned so that {111} plane of each AuNP is parallel to that of the others in Fig. 9(b). After the cold welding shown in Fig. 9(d), {100} planes are found in the z-directional section of top and bottom AuNPs. In the middle AuNP, {211} planes are found everywhere except for the stacking fault region as shown in the contour of centro-symmetry parameter.
In summary, the DEP-assisted cold welding forms straight nanoribbons adjusting lattice structures. The cold-welding of AuNPs generally occurs in a radial and in-plane direction by the interactions with mica substrate. In the presence of DEP forces, however, cold-welding is directed to the direction of electric field. It turns out that  www.nature.com/scientificreports www.nature.com/scientificreports/ the welded region is nearly perfect to provide the same crystal orientation and strength as the rest of nanostructures, which can be extensively utilized in the fabrication of various nanostructures.

experiment. (Preparation of green tea extract)
Dried green tea leaves used in the present study were a donation from the Institute of Hadong Green Tea (Hadong, Gyeongnam, Republic of Korea). The dried leaves were pulverized by using a blender and deionized water (2 L) was added to the pulverized leaves (200 g). Sonication was conducted at ambient temperature for 1 h to extract materials. The extraction process was repeated three times. Water fraction containing extracted materials was pooled and filtered using Whatman filter papers. Centrifugation was performed (3,000 g force, 18 °C, 25 min) and the supernatant was pooled. The pooled supernatant was subjected to syringe-filter and the filtered solution was freeze-dried. The freeze-dried powder was dissolved in de-ionized water to make a final concentration of 2% (w/v). This solution was used as a stock solution and utilized for the green synthesis.
(Green synthesis using green tea extract) For the green synthesis 18 of AuNPs, gold (III) chloride trihydrate (HAuCl 4 ·3H 2 O) was purchased from Sigma-Aldrich (St. Louis, MO, USA). The mixture of the extract (final concentration of 0.03%), hydrochloroauric acid trihydrate (final concentration of 0.5 mM) and sodium hydroxide (final concentration of 1 mM) was prepared in deionized water (final volume 2 mL). Then the mixture was incubated in a 80 °C dry oven for 2 h. The mixture was subjected to centrifugation (14,000 g force, 20 °C, 20 min). The supernatant was removed and the pellet was re-dispersed with the same volume of deionized water.
(DEP on mica substrate) The synthesized AuNP suspension was loaded onto the following substrates and dried at ambient temperature overnight.
• TEM grid (a carbon-coated copper grid; carbon type-B, 300 mesh copper grid, Ted Pella, Inc., Redding, CA, USA). The AuNP suspension was pipetted onto the TEM grid.  www.nature.com/scientificreports www.nature.com/scientificreports/ AuNP suspension was pipetted onto the top of the mica to avoid direct contact with the electrodes. A 1~20 V peak-to-peak sinusoidal signal of frequency between 100 Hz and 10 MHz was applied to the electrodes (SIGLENT function generator; Dual-channel, with bandwidth up to 60 MHz, and amplitude up to 20 V pp .) • To characterize the nanostructures using spectrum techniques, K-Alpha X-ray Photoelectron Spectrometer (XPS) System was performed with a monochromatic Al Kα radiation of energy 1,486.6 eV (Thermo Fisher Scientific, UK). X-ray energy used was 12 kV and 72 W. • The major peaks were originated from the mica and the remaining reducing agent. The peaks for C 1 s, N 1 s, O 1 s, Si 2p, and Al 2p were from the mica substrate. A small peak of Au 4 f was observed. As shown in Fig. 10, doublet photoelectron peaks of Au 4 f were composed of Au 4f 7/2 at 84.7 eV and Au 4f 5/2 at 88.3 eV. These peaks can be assigned to Au(0) of nanoribbons.

MD simulation.
To verify the effects of the electric field on the AuNPs on mica substrate, MD simulations are performed using the LAMMPS code with time steps of 0.5 fs. The MD numerical model for mica substrate is constructed, based on ref. 16 .
(Application of forces) On the surface of the AuNPs, the induced charge distribution is considered. Since the charged surface atoms are subjected to additional forces like Lorentz and Coulomb forces, the motion of AuNPs is affected by the external electric field. πε ω = ∇ . If the gradient of the electric field is small, all the AuNPs in the electric field are subjected to homogeneous DEP forces which do not contribute to the aggregation of AuNPs. Also, when it comes to MD simulations, the interaction between the atoms in the AuNPs should be taken into account. The computation procedure of Coulomb forces due to the charge of AuNPs induced from the given electric field has been embedded in the LAMMPS code (Refer to Supplement: Charge distribution method for details). A charge distribution method is developed, based on the electrostatic shielding that the electric field disappears at the internal atoms of a metal nanoparticle subjected to an electric field. The first step is to identify the surface atoms in the AuNP, which is easily carried out by www.nature.com/scientificreports www.nature.com/scientificreports/ examining the magnitude of interaction potential energy in each atom of the AuNP since the metal nanoparticle maintains the lattice structure and the interaction potential energy tends to increase at surface atoms. Free electron distribution in an AuNP induces the charge distribution, which can be obtained by solving a linear system that enforces the overall electric field disappears inside the AuNP. The atoms in the AuNP are subjected to the following forces; F F F F F , Au EAM m ica L orentz Coulumb = + + + where F EAM is from surrounding Au atoms, F mica is from mica substrate, Lorentz force F Lotentz in electric field, and F Coulomb between charged atoms. F Lotentz is eliminated since the overall charge of each AuNP is equal to zero and F EAM has little effect due to the long distance between the AuNPs. Thus, the interactions between AuNP-AuNP occur only by the F mica and F Coulomb .
(MD Simulation) Seven AuNPs of fcc lattice structure (lattice constant  4 078 A . ) are modeled to be attached to the mica substrate. The AuNPs are attached to the surface of mica substrate by the exchange mechanism of potassium metal ion and the AuNPs. The necessary potential parameters for the mica substrate are obtained from refs [22][23][24] . Periodic boundary conditions are imposed in the x and y directions. We construct a unit cell of mica substrate that can be extensively used according to the size and the number of AuNPs. The MD simulations are performed under the condition that atoms within 1 nm from the bottom are fixed and the others are free to move. An energy minimization of the MD system is conducted using a steepest descent algorithm. Furthermore, to remove the instability of the system, an isothermal (NVT) simulation is conducted for 100 ps at 300 K with a time step of 0.5 fs. After thermal equilibrium, an electric field of  0 05(V/A) . is applied to the lateral direction. Since the sample of AuNP suspension is dried on mica at an ambient temperature in real experiments, a Nose-Hoover thermostat is introduced to keep the temperature at 300 K in a canonical ensemble.

Data Availability
All data are available in the manuscript or the Supplementary Materials.