High throughput nanofabrication of silicon nanowire and carbon nanotube tips on AFM probes by stencil-deposited catalysts

A new and versatile technique for the wafer scale nanofabrication of silicon nanowire (SiNW) and multiwalled carbon nanotube (MWNT) tips on atomic force microscope (AFM) probes is presented. Catalyst material for the SiNW and MWNT growth was deposited on prefabricated AFM probes using aligned wafer scale nanostencil lithography. Individual vertical SiNWs were grown epitaxially by a catalytic vapor-liquid-solid (VLS) process and MWNTs were grown by a plasma-enhanced chemical vapor (PECVD) process on the AFM probes. The AFM probes were tested for imaging micrometers-deep trenches, where they demonstrated a significantly better performance than commercial high aspect ratio tips. Our method demonstrates a reliable and cost-efficient route toward wafer scale manufacturing of SiNW and MWNT AFM probes.     

Growth of poly-crystalline silicon-germanium on silicon by aluminum-induced crystallization

The formation of poly-crystalline silicon-germanium films on single-crystalline silicon substrates by the method of aluminum-induced crystallization was investigated. The aluminum and germanium films were evaporated onto the single-crystalline silicon substrate to form an amorphous-germanium/aluminum/single-crystalline silicon structure that was annealed at 450 °C-550 °C for 0-3 h. The structural properties of the films were examined using x-ray diffraction, Raman spectroscopy and Auger electron spectroscopy. The x-ray diffraction patterns confirmed that the initial transition from an amorphous to a poly-crystalline structure occurs after 20 min of aluminum-induced crystallization annealing process at 450 °C. The micro-Raman spectral analysis showed that the aluminum-induced crystallization process yields a better poly-crystalline SiGe film when the film is annealed at 450 °C for 40 min. The growth mechanism of the poly-crystalline silicon-germanium by aluminum-induced crystallization was also studied and is discussed.     

Boron induced recrystallization of amorphous silicon film by a rapid thermal process

Rapid thermal process (RTP) is to induce boron-doped amorphous silicon into a high degree of crystallization of polycrystalline silicon in 5 min. In addition to the short time characteristic, it also provides a relatively lower temperature route to prepare high percentage of polycrystalline silicon in comparison with solid phase crystallization method. Before RTP, boron is homogeneously doped into the amorphous silicon film by ion implantation technology. After rapid thermal processing, the grain size of the polycrystalline silicon was found about at 0.1-0.5 μm. The degree crystallization of silicon is reached up to 99.1% with a good hole mobility of 138.6 cm²/V s.     

In-situ observation of phase transformation in amorphous silicon during Joule-heating induced crystallization process

During the Joule-heating induced crystallization (JIC) process of amorphous silicon for display applications, its phase transformation from amorphous to polycrystalline phases occurs through two different kinetic paths of either solid-to-solid or solid-to-liquid-to-solid phases. Depending on input conditions such as power density and pulsing time, each path results in nano-crystalline silicon phases or large grain structures produced by lateral growth, respectively. In this study, the phase-transformation phenomena during the JIC process were detected electrically and optically by the in-situ measurements of input voltage/current and normal reflectance at wavelength of 532 nm. The temperature field estimated from a simple conduction model confirms the phase-transformation behavior observed experimentally. In addition we could obtain the poly-Si structure produced by solid phase crystallization having the process time of 250 μs and reaching the highest temperature around 1350 K.     

Fabrication of polycrystalline silicon thin films on glass substrates using fiber laser crystallization

Laser crystallization of amorphous silicon (a-Si), using a fiber laser of λ = 1064 nm wavelength, was investigated. a-Si films with 50 nm thickness deposited on glass were prepared by a plasma enhanced chemical vapor deposition. The infrared fundamental wave (λ = 1064 nm) is not absorbed by amorphous silicon (a-Si) films. Thus, different types of capping layers (a-CeO_x, a-SiN_x, and a-SiO_x) with a desired refractive index, n and thickness, d were deposited on the a-Si surface. Crystallization was a function of laser energy density, and was performed using a fiber laser. The structural properties of the crystallized films were measured via Raman spectra, a scanning electron microscope (SEM), and an atomic force microscope (AFM). The relationship between film transmittance and crystallinity was discussed. As the laser energy density increased from 10-40 W, crystallinity increased from 0-90%. However, the higher laser density adversely affected surface roughness and uniformity of the grain size. We found that favorable crystallization and uniformity could be accomplished at the lower energy density of 30 W with a-SiO_x as the capping layer.     

Atomic force microscopy indentation of fluorocarbon thin films fabricated by plasma enhanced chemical deposition at low radio frequency power

Atomic force microscopy (AFM) indentation technique is used for characterization of mechanical properties of fluorocarbon (CF_x) thin films obtained from C₄F₈ gas by plasma enhanced chemical vapour deposition at low r.f. power (5-30 W) and d.c. bias potential (10-80 V). This particular deposition method renders films with good hydrophobic property and high plastic compliance. Commercially available AFM probes with stiff cantilevers (10-20 N/m) and silicon sharpened tips (tip radius < 10 nm) are used for indentations and imaging of the resulted indentation imprints. Force depth curves and imprint characteristics are used for determination of film hardness, elasticity modulus and plasticity index. The measurements show that the decrease of the discharge power results in deposition of films with decreased hardness and stiffness and increased plasticity index. Nanolithography based on AFM indentation is demonstrated on thin films (thickness of 40 nm) with good plastic compliance.     

Solid phase epitaxy of silicon thin films by diode laser irradiation for photovoltaic applications

High temperature solid phase epitaxial crystallization of amorphous silicon layers prepared by electron beam evaporation is investigated. By using a continuous wave diode laser for heating the films rapidly (in milliseconds to seconds) this method is suitable on glass substrates with low temperature resistance. Therefore, the method is an economically advantageous technique of producing absorber layers for thin film solar cells. For the experiments 500 nm of amorphous silicon was deposited on two different configurations of substrates. In the first one monocrystalline wafers of three different crystallographic orientations were used. In the second one a polycrystalline seed layer prepared on borosilicate glass served as substrate. The crystallization process was monitored in situ by time resolved reflectivity measurements. Depending on the crystal orientation 2 s to 3 s was needed for complete solid phase epitaxial crystallization of the amorphous films. The evolution of temperature during crystallization was simulated numerically.     

Toward wafer-scale patterning of freestanding intermetallic nanowires

Individual metal alloy nanowires of constant diameter and high aspect ratio have previously been self-assembled at selected locations on atomic force microscope (AFM) probes by the method reported in Yazdanpanah et al (2005 J. Appl. Phys. 98 073510). This process relies on the room temperature crystallization of an ordered phase of silver-gallium. A parallel version of this method has been implemented in which a substrate, either an array of micromachined tips (similar to tips on AFM probes) or a lithographically patterned planar substrate, is brought into contact with a continuous, nearly planar film of melted gallium. In several runs, freestanding wires are fabricated with diameters of 40-400 nm, lengths of 4-80 μm, growth rates of 80-170 nm s( - 1) and, most significantly, with yields of up to 97% in an array of 422 growth sites. These results demonstrate the feasibility of developing a batch manufacturing process for the decoration of wafers of AFM tips and other structures with selectively patterned freestanding nanowires.     

Crystallization of amorphous silicon thin films: The effect of rapid thermal processing pretreatment

In the present work, the effect of low temperature short-time rapid thermal processing (RTP) pretreatment on the average grain size and the crystallinity of the polycrystalline silicon thin films, fabricated by subsequent solid phase crystallization (SPC) of amorphous silicon (a-Si) thin films grown by radio-frequency plasma-enhanced chemical vapor deposition (RF-PECVD) at high temperature has been studied. The average grain size and the crystallinity results were estimated using X-ray diffraction (XRD) and Raman spectroscopy, respectively. It was found that RTP at 800 °C for 60 s resulted in slightly larger average grain size and higher crystallinity than those without the RTP pretreatment after SPC at 800 °C for 5, 10 and 22 h. The results suggest that the low-temperature short-time RTP pretreatment can promote the crystallization process of the as-deposited a-Si thin films during the following SPC and then improve their crystallinity. Finally, the mechanism is also discussed in detail in the paper.     

Batch fabrication of atomic force microscopy probes with recessed integrated ring microelectrodes at a wafer level

A batch fabrication process at the wafer-level integrating ring microelectrodes into atomic force microscopy (AFM) tips is presented. The fabrication process results in bifunctional scanning probes combining atomic force microscopy with scanning electrochemical microscopy (AFM-SECM) with a ring microelectrode integrated at a defined distance above the apex of the AFM tip. Silicon carbide is used as AFM tip material, resulting in reduced mechanical tip wear for extended usage. The presented approach for the probe fabrication is based on batch processing using standard microfabrication techniques, which provides bifunctional scanning probes at a wafer scale and at low cost. Additional benefits of batch fabrication include the high processing reproducibility, uniformity, and tuning of the physical properties of the cantilever for optimized AFM dynamic mode operation. The performance of batch-fabricated bifunctional probes was demonstrated by simultaneous imaging micropatterned platinum structures at a silicon dioxide substrate in intermittent (dynamic) and contact mode, respectively, and feedback mode SECM. In both, intermittent and contact mode, the bifunctional probes provided reliable correlated electrochemical and topographical data. In addition, simulations of the diffusion-limited steady-state currents at the integrated electrode using finite element methods were performed for characterizing the developed probes.     

Microwave-crystallization of amorphous silicon film using carbon-overcoat as susceptor

Crystallization of amorphous silicon (a-Si:H) film is extremely important in many aspects of electronic devices and has been heavily explored. We demonstrate that microwave irradiation, 200 W, is able to fast-crystallize a-Si:H film using as susceptor carbon-overcoat which contains graphite and carbon nano-tube. X-ray diffraction and Raman spectra reveal that nearly full crystallization is reached within 90 s. Microwave absorption by the carbon-overcoat generates thermal energy which heats up a-Si:H film to a threshold temperature 440 ± 10 °C required for initiation of microwave crystallization. Dielectric properties of a-Si:H film facilitate its self-heating and nucleation of Si crystallites at above the threshold temperature. This method is extendable to fast-crystallize a-Si:H film on a remote and large-area basis.     

Highly conductive p-type nanocrystalline silicon films deposited by RF-PECVD using silane and trimethylboron mixtures at high pressure

In this paper we present a study of boron-doped nc-Si:H films prepared by PECVD at high deposition pressure (≥4 mbar), high plasma power and low substrate temperature (≤200 °C) using trimethylboron (TMB) as a dopant gas. The influence of deposition parameters on electrical, structural and optical properties is investigated. We determine the deposition conditions that lead to the formation of p-type nanocrystalline silicon thin films with very high crystallinity, high value of dark conductivity (>7 (Ω cm)⁻¹) and high optical band gap (≥1.7 eV). Modeling of ellipsometry spectra reveals that the film growth mechanism should proceed through a sub-surface layer mechanism that leads to silicon crystallization.The obtained films are very good candidates for application in amorphous and nanocrystalline silicon solar cells as a p-type window layer.     

Broadband and wide-angle antireflection subwavelength structures of Si by inductively coupled plasma etching using dewetted nanopatterns of Au thin films as masks

We report the broadband and wide-angle antireflection subwavelength structures (SWSs) on silicon (Si) substrate by inductively coupled plasma (ICP) etching using gold (Au) nanopatterns as etch masks. The reflectance depends strongly on the etched profile of Si SWSs which is influenced by both thermal dewetting and etching conditions. The size, shape, and array geometry of nano-sized patterns, which are produced via the thermal dewetting of Au thin films, are optimized under proper heat treatment. The etched depth and shape of Si nano tips are controlled additionally by ICP power, thus achieving the efficient antireflection characteristics. The optimized Si SWS with the tapered structure and sharp tips at high ICP power leads to a significantly low reflectance value of < 1% at wavelengths of 350-1100 nm. Furthermore, it exhibits a wide-angle antireflection property of < 7.5% at incident angles of 8-70° over a wide wavelength range of 300-1100 nm.     

Plastic tip arrays for force spectroscopy

The mechanical stability and viability of molecules investigated with the atomic force microscope (AFM) continue to be limiting factors in the duration of force spectroscopy measurements. In an effort to circumvent this problem, we have fabricated an all-plastic array of over 30 000 tips with dimensions similar to common AFM probes using silicon micromolding techniques. This approach enables rapid fabrication of tip arrays with improved properties, as compared to tip arrays made entirely of silicon.     

Fabrication and characterization of a silicon cantilever probe with an integrated quartz-glass (fused-silica) tip for scanning near-field optical microscopy

A cantilever-based probe is introduced for use in scanning near-field optical microscopy (SNOM) combined with scanning atomic-force microscopy (AFM). The probes consist of silicon cantilevers with integrated 25-mum-high fused-silica tips. The probes are batch fabricated by microfabrication technology. Transmission electron microscopy reveals that the transparent quartz tips are completely covered with an opaque aluminum layer before the SNOM measurement. Static and dynamic AFM imaging was performed. SNOM imaging in transmission mode of single fluorescent molecules shows an optical resolution better than 32 nm.     

Piezoresistive polysilicon film obtained by low-temperature aluminum-induced crystallization

A low-temperature deposition process employing aluminum-induced crystallization has been developed for fabrication of piezoresistive polycrystalline silicon (polysilicon) films on low cost and flexible polyimide substrates for force and pressure sensing applications. To test the piezoresistive properties of the polysilicon films, prototype pressure sensors were fabricated on surface-micromachined silicon nitride (Si₃N₄) diaphragms, in a half-Wheatstone bridge configuration. Characterization of the pressure sensor was performed using atomic force microscope in contact mode with a specially modified probe-tip. Low pressure values ranging from 5 kPa to 45 kPa were achieved by this method. The resistance change was found to be − 0.1% to 0.5% and 0.07% to 0.3% for polysilicon films obtained at 500 °C and 400 °C, respectively, for the applied pressure range.     

Growth of vertically aligned arrays of carbon nanotubes for high field emission

Vertically aligned multi-walled carbon nanotubes have been grown on Ni-coated silicon substrates, by using either direct current diode or triode plasma-enhanced chemical vapor deposition at low temperature (around 620 °C). Acetylene gas has been used as the carbon source while ammonia and hydrogen have been used for etching. However densely packed (∼ 10⁹ cm^− 2) CNTs were obtained when the pressure was ∼ 100 Pa. The alignment of nanotubes is a necessary, but not a sufficient condition in order to get an efficient electron emission: the growth of nanotubes should be controlled along regular arrays, in order to minimize the electrostatic interactions between them. So a three dimensional numerical simulation has been developed to calculate the local electric field in the vicinity of the tips for a finite square array of nanotubes and thus to calculate the maximum of the electron emission current density as a function of the spacing between nanotubes. Finally the triode plasma-enhanced process combined with pre-patterned catalyst films (using different lithography techniques) has been chosen in order to grow regular arrays of aligned CNTs with different pitches in the micrometer range. The comparison between the experimental and the simulation data permits to define the most efficient CNT-based electron field emitters.     

Field emission characteristics of an individual carbon nanotube inside a field emission-scanning electron microscope

Field emission (FE) properties of individual single-walled carbon nanotubes (SWCNT) were investigated inside a field emission-scanning electron microscopy. The individual SWCNT turned on a voltage of 23 V defined to produce a current of 10 pA, and was saturated at around 43 V and 880 nA. The FE characteristic of individual SWCNT also followed a conventional Fowler-Nordheim (F-N) theory in which a single linear slope in the F-N plots is measured below their limit of current level corresponding to the saturation regime of emission current. Energy-dispersive X-ray spectroscopy analysis showed that carbon atoms were deposited on the anode surface by the local heating of SWCNT tip during the FE processes and indicated about atomic 83% of carbon atoms. The carbon atoms were newly found to be evaporated and deposited on the anode surface during the FE process such that it was assumed that the degradation of FE was caused by evaporation and deposition of carbon atoms during the FE process.     

The SERS and TERS effects obtained by gold droplets on top of Si nanowires

We show that hemispherical gold droplets on top of silicon nanowires when grown by the vapor-liquid-solid (VLS) mechanism, can produce a significant enhancement of Raman scattered signals. Signal enhancement for a few or even just single gold droplets is demonstrated by analyzing the enhanced Raman signature of malachite green molecules. For this experiment, trenches (approximately 800 nm wide) were etched in a silicon-on-insulator (SOI) wafer along <110> crystallographic directions that constitute sidewalls ({110} surfaces) suitable for the growth of silicon nanowires in <111> directions with the intention that the gold droplets on the silicon nanowires can meet somewhere in the trench when growth time is carefully selected. Another way to realize gold nanostructures in close vicinity is to attach a silicon nanowire with a gold droplet onto an atomic force microscopy (AFM) tip and to bring this tip toward another gold-coated AFM tip where malachite green molecules were deposited prior to the measurements. In both experiments, signal enhancement of characteristic Raman bands of malachite green molecules was observed. This indicates that silicon nanowires with gold droplets atop can act as efficient probes for tip-enhanced Raman spectroscopy (TERS). In our article, we show that a nanowire TERS probe can be fabricated by welding nanowires with gold droplets to AFM tips in a scanning electron microscope (SEM). TERS tips made from nanowires could improve the spatial resolution of Raman spectroscopy so that measurements on the nanometer scale are possible.     

Transmission electron microscopy study of Ni–Si nanocomposite films

Nickel induced crystallization of amorphous Si (a-Si) films is investigated using transmission electron microscopy. Metal-induced crystallization was achieved on layered films deposited onto thermally oxidized Si(3 1 1) substrates by electron beam evaporation of a-Si (400 nm) over Ni (50 nm). The multi-layer stack was subjected to post-deposition annealing at 200 and 600 °C for 1 h after the deposition. Microstructural studies reveal the formation of nanosized grains separated by dendritic channels of 5 nm width and 400 nm length. Electron diffraction on selected points within these nanostructured regions shows the presence of face centered cubic NiSi₂ and diamond cubic structured Si. Z-contrast scanning transmission electron microscopy images reveal that the crystallization of Si occurs at the interface between the grains of NiSi₂ and a-Si. X-ray absorption fine structure spectroscopy analysis has been carried out to understand the nature of Ni in the Ni–Si nanocomposite film. The results of the present study indicate that the metal induced crystallization is due to the diffusion of Ni into the a-Si matrix, which then reacts to form nickel silicide at temperatures of the order of 600 °C leading to crystallization of a-Si at the silicide–silicon interface.