STEM observation of tungsten tips sharpened by field-assisted oxygen etching

Tungsten tips oriented toward the <111> direction were fabricated by field-assisted O₂ etching, and observed by means of scanning transmission electron microscopy (STEM) and field ion microscopy (FIM). The radii of curvature of the tip apexes were sharpened from 16–20 nm to less than 2 nm. The O₂ etching is considered to start from the O₂ imaging region depending on the field distribution around the tip apex and shank. We estimated the effect of field distribution derived from a shank shape and applied bias voltage. The results showed that the tip with a cylindrical shank before the O₂ etching became sharper than tips having an initial paraboloidal shape, with respective cone angles (defined in Fig. 3) of 58° and 80°. The field emission (FE) patterns of these etched tips became a single spot derived from the W(111) plane, and their opening angles (defined by the full width at half maximum) were 14.4° and 7.8°, respectively.     

High speed sub-micrometric microscopy using optical polymer microlens

We report the high speed scanning submicronic microscopy （SSM） using a low cost polymer microlens integrated at the extremity of an optical fiber. These microlenses are fabricated by a free-radical photopolymerization method. Using a polymer microlens with a radius of curvature of 250 nm, a sub-micrometric gold pattern is imaged experimentally by SSM. Different distances between the tip and the sample are used with a high scanning speed of 200 cm/s. In particular, metallic absorption contrasts are described with an optical spatial resolution of 250 nm at the wavelength of 532 nm. Moreover, finite-difference time-domain （FDTD） simulations concerning the focal lengths of microlenses with different geometries and heights support the experimental data.     

ITO: Zr bi-layers deposited by reactive O2 and Ar plasma with high work function for silicon heterojunction solar cells

We report the influence of reactive oxygen (O₂) and argon (Ar) plasma based ITO:Zr bi-layers for silicon heterojunction (SHJ) solar cells. The purpose of reactive O₂ sputtered ITO:Zr was to improve the Hall mobility and work function while the Ar based ITO:Zr films play an important role to maintain good electrical characteristics. The thickness of reactive O₂ based ITO:Zr films was fixed at 15 nm while Ar based films was varied from 65 to 125 nm, respectively. ITO:Zr bi-layers with the thickness of 15/105 nm deposited by O₂ and Ar plasma, respectively, showed lowest resistivity of 2.358 × 10⁻⁴ Ω cm and high Hall mobility of 39.3 cm²/V · s. All ITO:Zr bi-layers showed an average transmittance of above 80% in the visible wavelength (380–800 nm) region. Work function of ITO:Zr bi-layers was calculated from the X-ray photoelectron spectroscopic (XPS) data. The ITO:Zr work function was enhanced from 5.3 eV to 5.16 eV with the variation of ITO:Zr bi-layers from 15/65 to 15/125 nm, respectively. Front barrier height in SHJ solar cells can be modified by using TCO films with high work function. The SHJ solar cells were fabricated by employing the ITO:Zr bi-layer as front anti-reflection coating. The SHJ solar cells fabricated on ITO:Zr bi-layer with the thickness of 15/105 nm showed the best photo-voltage parameters as; V_oc = 739 mV, J_sc = 39.12 mA/cm², FF = 75.97%, η = 21.96%.     

Polymer tips for application of atomic force microscopy

A hydrophobic polymer tip for atomic force microscopy has been fabricated by two-photon adsorbed photopolymerization techniques and has been applied for the high resolution imaging of a hydrophilic metal surface. Using optimized photopolymerization conditions, we have succeeded in fabricating sub-100-nm sized polymer tips. This fabricating resolution of two-photon adsorbed photopolymerization is also confirmed by other supporting experiments. The imaging results show that the capillary-force-induced image distortion can be successfully removed by applying a pure hydrophobic polymer tip with a lateral resolution better than 5 nm, which is difficult to achieve with a commercial tip without any environmental control.     

Magnetic multilayers on nanosphere arrays with various curvature radius

[Co/Pt]_n multilayers with different Co thickness have been deposited on a silicon (Si) substrate to obtain better perpendicular anisotropy. The 0.5 nm thickness of the Co layer was chosen as the optimized thickness of the multilayer. Magnetic nanostructures with cap configuration were fabricated based on the template of polystyrene (PS) colloid sphere arrays with various curvature radius. Compared to the flat multilayer, the cap multilayer showed an oblique average anisotropy axis. When the curvature radius of the colloidal sphere increased, the shape of the multilayers changed from ellipsoidal to spherical, which led to a different dependence of magnetic properties on the field angles. The varying shape anisotropy, the dipole-dipole interaction between small magnetic caps, and the special nucleation mechanism on the spheres larger than 400 nm caused the M_r/M_s ratio and the coercivity to first increase and then decrease with varying curvature radius of the PS spheres.     

Wet-etching fabrication of multilayer GaAlAs/GaAs microtips for scanning near-field optical microscopy

We propose to fabricate GaAlAs/GaAs multilayer microtips for scanning near-field optical microscopy (SNOM) using anisotropic etching. The etching was performed in a solution of H₃PO₄:H₂O₂:H₂O operating at a temperature of 10 °C. We obtained pyramid-shaped microtips with four etched facets and with a radius of curvature at the apex that was lower than 50 nm.     

High-throughput fabrication of TERS probes using DC bias

Tip-enhanced Raman spectroscopy (TERS) has gained great attentions for sensitive characterization and super-resolution chemical imaging of various materials. The performance of TERS is mainly affected by the probe geometry, such as the diameter of the tip apex, surface roughness, etc. In this regard, the fabrication of a sharp apex from metal wire is the one of the most important factor for TERS experiments. Conventionally, the electrochemical etching is commonly used technique for fabricating those metallic probes. To avoid the surface defects, the pulsed bias was commonly employed in the electrochemical etching process. However, it would make the fabrication system to be complex and sophisticated. Here, we report an simple automated electrochemical etching systems using DC bias for the efficient fabrication of TERS probes. With our optimized condition for DC electrochemical etching, gold probes with a clean surface and a radius of curvature below 200 nm can be obtained with yield of 85%. The fabricated metallic probe is used to detect the brilliant cresyl blue (BCB) molecules on the gold film, and it is confirmed that the enhancement factor is about 3,400.     

Electrochemical fabrication of silver tips for tip‐enhanced Raman spectroscopy assisted by a machine vision system

Both tip‐enhanced Raman spectroscopy and scanning tunneling microscopy require the use of sharp tips. Electrochemical etching appears to be the most widely used method for preparing tips. To address the over‐etching problem associated with the silver tips by either using voltage or current as a feedback, we developed here an optical method‐based machine vision to achieve a quick cutoff of the circuit once the tip forms. It is a fully automated method with a response time of about 40 ms and is tolerated with any existing electrochemical etching method. We can significantly decrease the time of over‐etching of the silver tip when short rectangular pulses with a duty cycle of 28.6% were used. The mean radius of curvature was ca. 58 nm, as measured from over 50 tips. The capacities of silver tips for high‐resolution scanning tunneling microscopy imaging and high‐sensitivity tip‐enhanced Raman studies have been demonstrated. Copyright © 2016 John Wiley & Sons, Ltd.     

Electroless Nickel Plating under Continuous Ultrasonic Irradiation to Fabricate a Near-Field Probe Whose Metal Coat Decreases in Thickness toward the Tip

This paper describes a size-dependent electroless plating method to fabricate a new type of probe with a locally decreasing thickness of metal and a tiny tip size for a combined high resolution shear-force and near-field optical microscope. In this method, the tip size and decreasing thickness profile, which affect the resolution capabilities of the microscopes, are controlled by adding a continuous ultrasonic wave with a frequency of 1 MHz to a nickel plating bath. The probe with a tip radius of curvature of 25 nm was successfully fabricated at an ultrasonic power density of 1.6 W cm⁻², its metal thickness gradually decreased from 850 to 20 nm toward the distal tip.     

Synthesis and characterization of “mulberry”-like Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/multiwalled carbon nanotube nanocomposites

Nanocomposites composed of multi-wall carbon nanotubes (MWNTs) and Fe₃O₄ nanoparticles were fabricated using solvothermal method. Transmission and scanning electron microscopy, energy dispersive spectroscopy, and X-ray powder diffraction measurements confirmed that these mulberry-like Fe₃O₄ microparticles which were combined with the MWNTs in a random pattern are constructed with tiny nanocrystallites (12 nm in average diameter). The magnetic properties of the Fe₃O₄/MWNTs nanocomposites were measured using a vibrating sample magnetometer. Results showed that the Fe₃O₄/MWNTs nanocomposites exhibited superparamagnetism at room temperature and possessed a lower saturation magnetization (around 27.6 emu/g) than that of the pure Fe₃O₄ nanoparticles (around 33.7 emu/g). The Fe₃O₄/MWNTs nanocomposites have potential applications in engineering and medicine.     

Design and Fabrication of Microlens Array for Near-Field Vertical Cavity Surface Emitting Laser Parallel Optical Head

A GaP microlens for collecting laser light was developed in the tip of a near-field probe. It is important to realize a near-field optical probe head with high throughput and a small spot size. The design and fabrication results of the GaP microlens array are described. The most suitable GaP microlens with a probe was calculated as having a 10 μm radius using the two-dimensional finite difference time domain (2-D FDTD) method. The full width half maximum (FWHM) spot size variation and optical power density tolerance were calculated as 157 nm ± 5 nm and 7%, respectively. A spherical GaP microlens was fabricated with a radius of 10 μm by controlling the Cl₂/Ar gas mixture ratio. The difference between the theoretical spherical shape and the fabricated GaP microlens was evaluated as 40 nm at peak to valley. The FWHM spot size and optical throughput of the fabricated microlens were measured as 520 nm and 63%, respectively. The microlens was the same as a theoretical lens with a 10 μm radius. The micron-lens array fabrication process for a near-field optical head was demonstrated in this experiment.     

Electro‐optic polymer/titanium dioxide hybrid core ring resonator modulators

Compact electro‐optic (EO) modulators are desirable for a number of applications. In this study, a ring modulator has been fabricated in the titanium dioxide (TiO₂) core and EO polymer cladding waveguide structure. A 250‐nm thick TiO₂ core was utilized to minimize the ring radius down to 100 μm, to avoid using the top cladding between the EO polymer and the electrode, and to improve the poling efficiency. The resonance obtained by the ring modulator was observed to shift by 0.02 nm/V due to the enhanced in‐device EO coefficient of 105 pm/V. A modulation depth of 3 dB was observed at the frequency response function at 20 kHz using 2‐V V_p–p clock signal.     

Facile synthesis and optical properties of Co3O4 nanostructures by the microwave route

Cobalt oxide (Co₃O₄) nanoplatelet shape like nanostructures have been successfully synthesized through a simple microwave route for the first time using cobalt acetate, NaOH and citric acid at 200 °C for 30 min. The structure and morphology of as-prepared Co₃O₄ nanoplatelets are characterized by means of powder X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), and scanning electron microscope (SEM). XRD measurements indicate that the product has a perfect crystalline cubic phase of Co₃O₄ with a lattice constant a=8.082 Å. The SEM images show that the obtained Co₃O₄ nanopowder consists of nanoplatelets with diameter 125 nm and thickness 20 nm. Energy-dispersive X-ray spectroscopy (EDS) show that the composition of Co₃O₄ is stoichiometric. Room temperature photoluminescence measurement is exhibited by a strong UV emission and a suppressed green emission, confirming the good optical properties for the as-prepared Co₃O₄ nanoplatelets.     

Fabrication of <1 1 0> oriented tungsten nano-tips by field-assisted water etching

We report the field-assisted H₂O etching that enabled us to fabricate nano-tips from polycrystalline <1 1 0> oriented tungsten wires at room temperature. We optimized the sharpening procedure in order to obtain field emissions (FEs) with high collimation. The typical tip apex was composed of a large base and a nano-protrusion with a radius of curvature less than 3.5 Å. The narrowest opening angle (full width at half maximum) of the FE was 4.3° at 150 pA. We prepared two types of tips using two different applied bias voltages during the H₂O etching. The electron microscope images and the analysis of Fowler-Nordheim (FN) plots revealed that the sizes of the individual bases depended on the fixed bias voltages during the H₂O etching and affected their FE properties. In addition, we could confirm that the FE current from the nano-tip was more stable than that of the normal tip.     

Improvement of performance of tetraphenylporphyrin-based red organic light emitting diodes using WO3 and C60 buffer layers

One of the porphyrin derivatives, meso-tetraphenylporphyrin (TPP), has been synthesized and examined as an emitter material (EM) for efficient fluorescent red organic light-emitting diodes (OLEDs). By inserting a tungsten oxide (WO₃) layer into the interface of anode (ITO) and hole transport layer N,N′-Di-[(1-napthyl)-N,N′-diphenyl]-(1,1′-biphenyl)-4,4′-diamine (NPB) and by using fullerene (C₆₀) in contact with a LiF/Al cathode, the performance of devices was markedly improved. The current density–voltage–luminance (J–V–L) characterizations of the samples show that red OLEDs with both WO₃ and C₆₀ as buffer layers have a lower driving voltage and higher luminance compared with the devices without buffer layers. The red OLED with the configuration ITO/WO₃ (3 nm)/NPB (50 nm)/TPP (60 nm)/BPhen (30 nm)/C₆₀ (5 nm)/LiF (0.8 nm)/Al (100 nm) achieved the high luminance of 6359 cd/m² at the low driving voltage of 8 V. At a current density of 20 mA/cm², a pure red emission with CIE coordinates of (0.65; 0.35) is observed for this device. Moreover, a power efficiency of 2.07 lm/W and a current efficiency of 5.17 cd/A at 20 mA/cm² were obtained for the fabricated devices. The study of the energy level diagram of the devices revealed that the improvement in performance of the devices with buffer layers could be attributed to lowering of carrier-injecting barrier and more balanced charge injection and transport properties.     

Bending effects and temperature dependence of magnetic properties in a Fe-rich amorphous wire

Amorphous wires with composition Fe_77.5Si_7.5B₁₅ exhibit a very peculiar magnetization process characterized by a single and quite large Barkhausen jump. This gives rise to a squared hysteresis loop at a critical magnetic field. The bistable behaviour, widely studied in wires with typical length of 10 cm and diameter of 125 μm, appears above a length of about 7 cm in straight wires and disappears for curvature radius within the range 2–12 cm in bent wires. In this work it is shown that bistability occurs in bent wires, whatever their curvature is, provided the wires are long enough. To this purpose spiral-shaped samples with several turns are considered. However, when the wire length is not a integer number of turns the magnetization reverses through many large Barkhausen jumps. In this condition, varying the measuring temperature can activate the energy barriers for the jumps.     

Fabrication of chain-like Mn2O3 nanostructures via thermal decomposition of manganese phthalate coordination polymers

A novel manganese coordination polymer [Mn(Pht)(H₂O)]_n as a precursor was obtained by chemical precipitation involving an aqueous solution of anhydrous manganese acetate and phthalate anion as a potential O-banded ligand. Fourier transform infrared (FT-IR) results proved that phthalate anions coordinate to metal cations as a chelating bidentate ligand, making polymeric structure. The Mn₂O₃ nanostructures have been prepared via thermal decomposition of as-prepared manganese phthalate polymers as precursor in the presence of oleic acid (OA) and triphenylphosphine (TPP) as a stabilizer and capping. Different approaches such as FT-IR, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were applied to characterize the products. TEM images and XRD analysis indicated that the as-synthesized chain-like Mn₂O₃ has a crystal phase of cubic syngony with a mean size of ∼40 nm.     

原子力显微镜加工红外微透镜阵列的研究

提出了利用原子力显微镜灰阶阳极氧化方法加工Si、Ge、GaAs等晶体材料为基础的红外微透镜阵列.加工了3×3的红外硅微透镜阵列,微透镜的高度和表面直径重复性误差分别为0.2nm和6.0 nm,微透镜的平均曲率半径为510.8 nm.分析了原子力显微镜加工红外微透镜产生面型结构误差的原因,并提出了减小面型结构误差的方法.利用此种方法加工的折射、衍射和混合红外微透镜阵列可以进一步缩小红外成像系统的尺寸.     

Confinement of the field electron emission to atomic sites on ultra sharp tips

The spatially controlled field assisted etching method for sharpening metallic tips, in a field ion microscope (FIM), is used to study the evolution of the field emission when the tip apex radius is decreased below 1 nm. Unlike the conventional image formation in a field emission microscope (FEM), we demonstrate that at this scale the field emission is rather confined to atomic sites. A single atom apex fabricated at the end of such tips exhibits an outstanding brightness compared to other atomic tips. The measurements have been repeated for two double atom tips, with different atom-atom separations, and images of atomic field emission localization have also been obtained. We have found that the field emission intensity alternates between adjacent atoms when the applied voltage is gradually increased beyond a threshold value.     

Nanoscale near-field infrared spectroscopic imaging of silica-shell/gold-core and pure silica nanoparticles

Spectroscopic near-field imaging of single silica-shell/Au-core and pure silica nanoparticles deposited on a silicon substrate is performed in the infrared wavelength range (λ = 9–11 μm) using scattering-type scanning near-field optical microscopy (s-SNOM). By tuning the wavelength of the incident light, we have acquired information on the spectral phonon–polariton resonant near-field interactions of the silica-shell/Au-core and pure silica nanoparticles with the probing tip. We made use of the enhanced near-field coupling between the high index Au-core and the probing tip to achieve spectral near-field contrast of the thin silica coating (thickness < 10 nm). Our results show that spectroscopic imaging of thin coating layers and complex core–shell nanoparticles can be directly performed by s-SNOM.