Femtosecond laser patterning of Ta0.1W0.9Ox/ITO thin film stack

Selective laser patterning of thin films in a multilayered structure is an emerging technology for process development and fabrication of optoelectronics and microelectronics devices. In this work, femtosecond laser patterning of electrochromic Ta_0.1W_0.9O_x film coated on ITO glass has been studied to understand the selective removal mechanism and to determine the optimal parameters for patterning process. A 775 nm Ti:sapphire laser with a pulse duration of 150 fs operating at 1 kHz was used to irradiate the thin film stacks with variations in process parameters such as laser fluence, feedrate and numerical aperture of objective lens. The surface morphologies of the laser irradiated regions have been examined using a scanning electron microscopy and an optical surface profiler. Morphological analysis indicates that the mechanism responsible for the removal of Ta_0.1W_0.9O_x thin films from the ITO glass is a combination of blistering and explosive fracture induced by abrupt thermal expansion. Although the pattern quality is divided into partial removal, complete removal, and ITO film damage, the ITO film surface is slightly melted even at the complete removal condition. Optimal process window, which results in complete removal of Ta_0.1W_0.9O_x thin film without ablation damage in the ITO layer, have been established. From this study, it is found that focusing lens with longer focal length is preferable for damage-free pattern generation and shorter machining time.     

Cluster size dependence of SiO2 thin film formation by O2 gas cluster ion beams

Cluster size effects of SiO₂ thin film formation with size-selected O₂ gas cluster ion beams (GCIBs) irradiation on Si surface were studied. The cluster size varied between 500 and 20,000 molecules/cluster. With acceleration voltage of 5 kV, the SiO₂ thickness was close to the native oxide thickness by irradiation of (O₂)_20,000 (0.25 eV/molecule), or (O₂)_10,000 (0.5 eV/molecule). However, it increased suddenly above 1 eV/molecule (5000 molecules/cluster), and increased monotonically up to 10 eV/molecule (500 molecules/cluster). The SiO₂ thickness with 1 and 10 eV/molecule O₂-GCIB were 2.1 and 5.0 nm, respectively. When the acceleration voltage was 30 kV, the SiO₂ thickness has a peak around 10 eV/molecule (3000 molecules/cluster), and it decreased gradually with increasing the energy/molecule. At high energy/molecule, physical sputtering effect became more dominant process than oxide formation. These results suggest that SiO₂ thin film formation can be controlled by energy per molecule.     

Patterning of amorphous and polycrystalline Ni78B14Si8 with a focused-ion-beam

The machining response of amorphous and crystalline Ni₇₈B₁₄Si₈ was investigated when structuring substrates using focused-ion-beam (FIB) milling. In particular, the sputtering yield as a function of the scan speed, and the effects of ion fluence and scan speed on the milled depth were studied. The ion fluence dependent evolution of the cross-sectional profiles of trenches was examined by atomic force microscopy (AFM). When milling amorphous Ni₇₈B₁₄Si₈, it was found that the sputtering yield first decreased with increasing the beam scan speed, then kept constant within the scan speed range, up to 710 nm/s, investigated in this work; it was also found that the milled depth was almost proportional to the ion beam fluence. The patterning of polycrystalline Ni₇₈B₁₄Si₈ resulted in anisotropic milling-rates due to the varying orientation of the grains in the material. The analysis of the profile evolution in both materials indicated that the surface finish of trenches was scan speed, ion beam fluence and scan strategy dependent. The study demonstrated that direct patterning by FIB could be used for producing masters in amorphous Ni-based alloys for injection moulding and hot embossing.     

Femtosecond laser micromilling of Si wafers

Femtosecond laser micromilling of silicon is investigated using a regeneratively amplified 775 nm Ti:Sapphire laser with a pulse duration of 150 fs operating at 1 kHz repetition rate. The morphological observation and topological analysis of craters fabricated by single-shot laser irradiation indicated that the material removal is thermal in nature and there are two distinct ablation regimes of low fluence and higher fluence with logarithmical relations between the ablation depth and the laser fluence. Crater patterns were categorized into four characteristic groups and their formation mechanisms were investigated. Femtosecond laser micromilling of pockets in silicon was performed. The effect of process parameters such as pulse energy, translation speed, and the number of passes on the material removal rate and the formation of cone-shaped microstructures were investigated. The results indicate that the microstructuring mechanism has a strong dependence on the polarization, the number of passes and laser fluence. The optimal laser fluence range for Si micromilling was found to be 2-8 J/cm² and the milling efficiency attains its maximum between 10 and 20 J/cm².     

Analyses of surface coloration on TiO2 film irradiated with excimer laser

TiO₂ film of around 850 nm in thickness was deposited on a soda-lime glass by PVD sputtering and irradiated using one pulse of krypton-fluorine (KrF) excimer laser (wavelength of 248 nm and pulse duration of 25 ns) with varying fluence. The color of the irradiated area became darker with increasing laser fluence. Irradiated surfaces were characterized using optical microscopy, scanning electron microscopy, Raman spectroscopy and atomic force microscopy. Surface undergoes thermal annealing at low laser fluence of 400 and 590 mJ/cm². Microcracks at medium laser fluence of 1000 mJ/cm² are attributed to surface melting and solidification. Hydrodynamic ablation is proposed to explain the formation of micropores and networks at higher laser fluence of 1100 and 1200 mJ/cm². The darkening effect is explained in terms of trapping of light in the surface defects formed rather than anatase to rutile phase transformation as reported by others. Controlled darkening of TiO₂ film might be used for adjustable filters.     

Structural characterization and ferromagnetic behavior of Fe-doped TiO2 powder by high-energy ball milling

Fe-doped TiO₂ powder was prepared by high-energy ball milling, using TiO₂ Degussa P-25 and α-Fe powders as the starting materials. The structure and magnetic properties of the Fe-doped TiO₂ powder were studied by X-ray diffraction, ⁵⁷Fe Mossbauer spectroscopy and vibrating sample magnetometer. The Reitveld refinement of XRD revealed that ball milling not only triggered incorporation of Fe in TiO₂ lattice but also induced the phase transformation from anatase to rutile in TiO₂ and consequently the milled Fe-doped TiO₂ powder contained only rutile.⁵⁷Fe Mössbauer effect measure showed that Fe atoms existed in Fe²⁺ and Fe³⁺ state, which were assigned to the solid solution Fe_xTi_1−xO₂. The magnetization measurements indicated that the milled Fe-doped TiO₂ powder was ferromagnetic above room temperature. The ferromagnetism in our milled Fe-doped TiO₂ powder seemingly does not come from Fe and iron oxides particles/clusters but from the Fe-doped TiO₂ powder matrices.     

Selective growth of carbon nantoubes on SiO2/Si substrate

Three-step raising temperature process was employed to fabricate carbon nanotubes by pyrolysis of ferrocene/melamine mixtures on silica and single crystalline silicon wafers respectively. Then the morphologies, structures and compositions of obtained carbon nanotubes are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscope (EDX) and electron energy-loss spectroscopy (EELS). TEM and SEM observation shows that on silica substrate, high-oriented carbon nanotube can grow compactly to form continuous film on both frontal and cross-section surfaces, but on silicon substrate, only can form on cross-section surface. These carbon nanotubes have much irregular cup-like structure, and with outer diameter varying from 25 nm to 35 nm. At the top end of carbon nanotube there is a catalyst particle. EDX analysis reveals that the particle are iron cluster, and EELS spectrum indicates that the nanotube is composed of pure carbon. Finally, the effect of substrate surface roughness on the growth behavior of carbon nanotubes has been discussed.     

The effect of silicon substrate on thickness of SiO2 thin film analysed by spectral reflectometry and interferometry

Techniques of spectral reflectometry and interferometry are used for measuring small changes in thickness of SiO₂ thin film grown by thermal oxidation on different silicon substrates. A slightly dispersive Michelson interferometer with one of its mirrors replaced by a thin-film structure is used to measure the reflectance and interferometric phase of the thin-film structure at the same time. The experimental data are used to determine precisely the thickness of the SiO₂ thin film on silicon wafers of two crystallographic orientations and different dopant concentrations. We confirmed very good agreement between the experimental data and theory and revealed that the thin-film thickness, which varies with the type of silicon substrate, depends linearly on the wavelength at which minimum in the spectral reflectance occurs. Similar behaviour was revealed for the interferometric phase.     

Ar irradiation of Si nanocrystal-doped SiO2: Evolution of photoluminescence

We report the evolution of photoluminescence (PL) of Si nanocrystals (nc-Si) embedded in a matrix of SiO₂ during Ar⁺ ion bombardment. The integrated intensity of nc-Si PL falls down drastically before the Ar⁺ ion fluence of 10¹⁵ ions cm⁻², and then decreases slowly with the increasing ion fluence. At the meantime, the PL peak position blueshifts steadily before the fluence of 10¹⁵ ions cm⁻², and then changes in an oscillatory manner. Also it is found that the nc-Si PL of the Ar⁺-irradiated sample can be partly recovered after annealing at 800 °C in nitrogen, but can be almost totally recovered after annealing in oxygen. The results confirm that the ion irradiation-induced defects are made up of oxygen vacancies, which absorb light strongly. The oscillatory peak shift of nc-Si can be related to a size-distance distribution of nc-Si in SiO₂.     

Nanostructuring Si surface and Si/SiO2 interface using porous-alumina-on-Si template technology. Electrical characterization of Si/SiO2 interface

In this work, anodic porous alumina thin films with pores in the nanometer range are grown on silicon by electrochemistry and are used as masking material for the nanopatterning of the silicon substrate. The pore diameter and density are controlled by the electrochemical process. Through the pores of the alumina film chemical oxidation of the silicon substrate is performed, leading to the formation of regular arrays of well-separated stoichiometric silicon dioxide nanodots on silicon, with a density following the alumina pores density and a diameter adjustable by adjusting the chemical oxidation time. The alumina film is dissolved chemically after the SiO₂ nanodots growth, revealing the arrays of silicon dioxide dots on silicon. In a next step, the nanodots are also removed, leaving a nanopatterned bare silicon surface with regular arrays of nanopits at the footprint of each nanodot. This silicon surface structuring finds interesting applications in nanoelectronics. One such application is in silicon nanocrystals memories, where the structuring of the oxidized silicon surface leads to the growth of discrete silicon nanocrystals of uniform size. In this work, we examine the electrical quality of the Si/SiO₂ interface of a nanostructured oxidized silicon surface fabricated as above and we find that it is appropriate for electronic applications (an interface trap density below 1–3×10¹⁰ eV⁻¹ cm⁻² is obtained, indicative of the high quality of the thermal silicon oxide).     

Perpendicular magnetic anisotropy of FePt film on Si substrate with SiO2 underlayer and B4C interlayers

FePt multilayer composite films with and without B₄C interlayer have been prepared by magnetron sputtering, respectively, and subsequent annealing in vacuum. It was found that the B₄C layers effectively serve as spacers to separate the FePt layers, enhancing (0 0 1) orientation of FePt alloy. Our results show that highly (0 0 1) oriented FePt/B₄C films have significant potential as perpendicular recording media.     

Layer uniformity in glucose oxidase immobilization on SiO2 surfaces

The goal of this work was the characterization, step by step, of the enzyme glucose oxidase (GOx) immobilization on silicon oxide surfaces, mainly by means of X-Ray photoelectron spectroscopy (XPS). The immobilization protocol consists of four steps: oxide activation, silanization, linker molecule deposition and GOx immobilization. The linker molecule, glutaraldehyde (GA) in this study, must be able to form a uniform layer on the sample surface in order to maximize the sites available for enzyme bonding and achieve the best enzyme deposition. Using a thin SiO₂ layer grown on Si wafers and following the XPS Si2p signal of the Si substrate during the immobilization steps, we demonstrated both the glutaraldehyde layer uniformity and the possibility to use XPS to monitor thin layer uniformity. In fact, the XPS substrate signal, not shielded by the oxide, is suppressed only when a uniform layer is deposited. The enzyme correct immobilization was monitored using the XPS C1s and N1s signals. Atomic force microscopy (AFM) measurements carried out on the same samples confirmed the results.     

Effects of interface between SnO2 thin film and Si substrate on growth time

SnO₂ thin film was grown on Si substrate using the low pressure chemical vapor deposition (LPCVD) method. The SnO₂ thin film was grown in the direction of (110) as deposition time increased. The atomic ratio of O decreased by 62.4, 57.6, and 45.6%, and the thickness of the thin film increased to 0.2, 0.3, and 0.7 ? as the deposition time increased to 10, 20, and 30 min, respectively. The interface of the thin film was examined using high-resolution transmission electron microscope (HRTEM) and energy dispersive spectroscopy (EDS) analysis. The SiO₂ layer was observed at between the SnO₂ thin film and the Si substrate. This layer decreased in thickness as the deposition time increased, which indicates that the deposition time affected the interface of the thin film.     

The effects of substrate temperature on the structure, morphology and photoluminescence properties of pulsed laser deposited SrAl2O4:Eu,Dy thin films

In this study, SrAl₂O₄:Eu²⁺,Dy³⁺ thin film phosphors were deposited on Si (1 0 0) substrates using the pulsed laser deposition (PLD) technique. The films were deposited at different substrate temperatures in the range of 40-700 °C. The structure, morphology and topography of the films were determined by using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). Photoluminescence (PL) data was collected in air at room temperature using a 325 nm He-Cd laser as an excitation source. The PL spectra of all the films were characterized by green phosphorescent photoluminescence at ∼530 nm. This emission was attributed to 4f⁶5d¹→4f⁷ transition of Eu²⁺. The highest PL intensity was observed from the films deposited at a substrate temperature of 400 °C. The effects of varying substrate temperature on the PL intensity were discussed.     

Synthesis and fine patterning of organic-inorganic composite SiO2-Al2O3 thick films

Organic-inorganic composite SiO₂-Al₂O₃ films have been prepared by sol-gel using methacryloxypropyl trimethoxysilane and aluminum sec-butoxide as the precursors. By introduction of organic groups into the inorganic backbone, the smooth and crack-free films could be readily achieved by a one-step dip-coating process, with the thickness up to 4.6 μm after being post-baked at 200 °C for 2 h. The films presented in an amorphous phase with an acceptable chemical homogeneity. Owing to the formation of chelate rings, the gel films showed a strong photosensitivity to ultraviolet light at 325 nm. The uniform fine patterns of SiO₂-Al₂O₃ thick films could be well defined by ultraviolet light imprinting simply using a mask. These performances of SiO₂-Al₂O₃ films indicate the potential for integrated optical systems.     

Interaction of O3+ Ions with Al2O3 Nanocapillaries

We investigate angular distributions of the transmitted 60 keV and 120 keV O^3＋ ions through nanocapillaries with 50hm diameter and 10μm length. The experimental results are in agreement with the ＇guiding effect＇ found by Stolterfoht et al. For different tilted angles of the nanocapillary membrane with respect to the beam, the angular distributions of the transmitted ions are measured by a one-dimensional micro-channel plate （MCP） detector. Moreover, the dependence of this guiding effect on the projectile energy is studied.     

Fabrication of ZnO/Al2O3 core-shell nanostructures and crystalline Al2O3 nanotube

We have demonstrated the crystalline ZnO-Al₂O₃ core-shell nanowire structure by atomic layer deposition (ALD) at a temperature 100 °C. The core-shell structure could have potential applications in the fabrication of ZnO field effect transistor. After dissolving the ZnO core, shape defined, rigid and robust crystalline Al₂O₃ shelled nanostructures have been fabricated. Nanowire ZnO nanostructures have been replicated by alumina shell. This is one of the most effective techniques for producing core-shell or shell/hollowed nanostructures of any desired objects. The Al₂O₃ shelled nanostructures could have potential applications as space confined nanoreactors, drug delivery, nanofluidic channels and optical transmitting.     

Photoluminescence of Si from Si nanocrystal-doped SiO2/Si multilayered sample

A multilayered Si nanocrystal-doped SiO₂/Si (or Si-nc:SiO₂/Si) sample structure is studied to acquire strong photoluminescence (PL) emission of Si via modulating excess Si concentration. The Si-nc:SiO₂ results from SiO thin film after thermal annealing. The total thickness of SiO layer remains 150 nm, and is partitioned equally into a number of sublayers (N = 3, 5, 10, or 30) by Si interlayers. For each N-layered sample, a maximal PL intensity of Si can be obtained via optimizing the thickness of Si interlayer (or d_Si). This maximal PL intensity varies with N, but the ratio of Si to O is nearly a constant. The brightest sample is found to be that of N = 10 and d_Si = 1 nm, whose PL intensity is ∼5 times that of N = 1 without additional Si doping, and ∼2.5 times that of Si-nc:SiO₂ prepared by co-evaporating of SiO and Si at the same optimized ratio of Si to O. Discussions are made based on PL, TEM, EDX and reflectance measurements.     

Crystalline orientation effects on conical structure formation in femtosecond laser irradiation of silicon and germanium

Irradiation of Si(1 0 0), Si(1 1 1), Si(1 1 0), Ge(1 0 0), and Ge(1 1 1) is compared for 150 fs, 800 nm wavelength pulses in a rough vacuum atmosphere. The surface crystalline orientation of the material is found to affect the final morphology, with (1 1 1)- and (1 1 0)-surface orientations exhibiting a much higher tendency for conical structure formation under multiple-pulse irradiation. Using cross-sectional transmission electron microscopy, the structures on Si(1 1 1) are found to have primarily crystalline cores with the same crystalline orientation as the substrate. The results show that the crystalline orientation of the target should be considered in laser machining applications.