High-resolution, resistless patterning of indium-tin-oxide thin films using excimer laser projection annealing process

High-resolution, large-area patterning of indium-tin-oxide (ITO) thin film was demonstrated using an excimer laser projection crystallization process. After amorphous ITO (a-ITO) was deposited on a glass substrate, the a-ITO was selectively crystallized using an excimer laser scanning projection exposure system. Following the selective crystallization, the substrate was dipped in an etchant for an optimized time, resulting in formation of high-resolution patterns of polycrystalline ITO (p-ITO) on the substrate because the a-ITO has higher etch rate than the p-ITO. The p-ITO patterns were clean and sharp, and the pattern quality was suitable for production applications in the microelectronics industry.     

Direct Laser Patterning of Soft Matter: Photothermal Processing of Supported Phospholipid Multilayers with Nanoscale Precision

Direct laser patterning of supported phospholipid multilayers is investigated. Spin coating is used to fabricate stacked bilayers of 1,2‐dioleoyl‐sn‐glycero‐3‐phosphate (DOPA). Photothermal processing with a focused laser beam at λ = 514 nm allows removal of the coating at predefined positions without causing any significant change in adjacent areas. Moreover, processing with nanoscale precision is feasible despite the soft and fluid nature of phospholipid films. In particular, holes with diameters from 1.8 µm down to 300 nm and below are fabricated by using a 1/e² laser spot size of about 2.5 µm. In addition, patterning is also very flexible and can be carried out over macroscopic length scales and at short processing times. Considering these features photothermal laser processing constitutes a powerful tool for micro‐ and nanopatterning of phospholipid films.     

Titanate nanotube coatings on biodegradable photopolymer scaffolds

Rigid, biodegradable photopolymer scaffolds were coated with titanate nanotubes (TNTs) by using a spin-coating method. TNTs were synthesized by a hydrothermal process at 150 °C under 4.7 bar ambient pressure. The biodegradable photopolymer scaffolds were produced by mask-assisted excimer laser photocuring at 308 nm. For scaffold coating, a stable ethanolic TNT sol was prepared by a simple colloid chemical route without the use of any binding compounds or additives. Scanning electron microscopy along with elemental analysis revealed that the scaffolds were homogenously coated by TNTs. The developed TNT coating can further improve the surface geometry of fabricated scaffolds, and therefore it can further increase the cell adhesion.     

氧化锌脱膜和激光刻蚀制备亚微米自支撑聚酰亚胺薄膜及其性能

探讨小于1 μm自支撑聚酰亚胺薄膜的制备及其性能。以稀盐酸为腐蚀剂, 对涂于氧化锌衬底上的聚酰胺酸薄膜进行剥离, 经热亚胺转化为聚酰亚胺薄膜, 再用准分子激光对其刻蚀减薄。采用原子力显微镜、傅里叶变换红外光谱仪和分光光度计对薄膜的微观结构和光谱性能进行了表征。结果表明, 以室温下溅射的氧化锌薄膜为脱膜剂, 制备了厚度约950 nm的自支撑薄膜, 而激光刻蚀使聚酰亚胺薄膜厚度减薄至150 nm。厚度分别为950和150 nm薄膜的红外谱中均出现了聚酰亚胺特征吸收峰(1775、1720、1380和725 cm^-1), 且两者在400~2500 nm范围的平均透过率分别为80.3% 和83.5%。     

Preparation and characterization of γ-MnO2/CNTs nanocomposite

A layer of manganese dioxides (γ-MnO₂) was adsorbed upon carbon nanotubes (CNTs) surface by using a chemical deposit process. The morphologies of the MnO₂/CNTs composite were characterized using transmission electron microscopy (TEM), energy-dispersive X-ray spectrometry (EDS), X-ray diffraction (XRD) and laser Raman spectroscopy (RS). It is found that the adsorbed layer belongs to the γ-MnO₂ nanoparticles in the size of about 10 nm, and coated homogeneously around the CNTs. It is expected that this γ-MnO₂/CNTs composite will be applied to make supercapacitors.     

Patterning ZnO layers with frequency doubled and quadrupled Nd:YAG laser for PV application

We report the feasibility of nanosecond laser patterning of ZnO layer in CIGS-based solar cells. Patterning the ZnO layer on top of the entire solar cell structure (i.e. substrate configuration), as well as scribing the transparent conducting oxide layer on glass substrate (i.e. superstrate configuration) was studied at frequency doubled and quadrupled Nd:YAG wavelengths. We found that the 100 nm ZnO/glass structure can easily be patterned by both wavelengths, while for the 1 μm thick layer better results were achieved with UV pulses. In the substrate configuration patterning with the visible laser permits controllable cutting, while even mild UV processing causes severe damage to the underlying CIGS layer.     

Design and fabrication of polymeric micro-optical components using excimer laser ablation

Abstract

Numerical simulation was used to predict the profile of a three-dimensional aspherical microlens and a microprism array. Based on the simulated results, the desired micro-optical lens profile was obtained using excimer laser ablated polyimide. The simulation method applied to excimer laser ablation can significantly reduce the quantity of microablation experiments. Ablated microstructures with surface roughness R _a < 20 nm were successfully achieved for micro-optical components. The excimer laser ablation parameters included laser fluence, shot number, workstation velocity, and repetition rate. Numerical simulation can be applied to predict various profiles of microlens and microprism arrays with different dimensions, the desired geometries being formed by laser ablation.     

Nanocrystalline silicon films formed under the impact of pulsed excimer laser radiation on polyimide substrates

Polycrystalline silicon films on polyimide substrates were obtained by a method based on the crystallization of amorphous films under the impact of nanosecond pulses of excimer laser radiation. Characteristics of the film structure were studied by methods of Raman scattering and high-resolution electron microscopy. For the laser crystallization regimes employed, nanocrystalline silicon films with an average grain size of 5 nm were obtained. The results are of interest for the development of large-scale microelectronic devices (active thin-film transistor matrices) on cheap flexible substrates.     

The effect of a compliant polyimide nanocoating on the tensile properties of a high strength PAN-based carbon fiber

The effect of a compliant polyimide nanocoating on the tensile strength of a polyacrylonitrile-based high tensile strength (T1000GB) carbon fiber was investigated. The pyromellitic dianhydride/4-4′-oxydianiline polyimide nanocoating was deposited by high-temperature vapor deposition polymerization. The thickness of the polyimide coating was about 100 nm. The tensile strength and Weibull modulus of nanocoated and uncoated fiber bundles were evaluated using a polyimide-impregnated bundle-composite. The results clearly demonstrated that the compliant polyimide nanocoating is effective in improving the tensile strength and Weibull modulus of T1000GB carbon fiber.     

Excimer laser ablation of single crystal 4H-SiC and 6H-SiC wafers

A 248 nm, 23 ns pulsed excimer laser was used to compare the ablation characteristics of single crystal wafers of the polytypes 4H-SiC and 6H-SiC over a wide range of energy fluence (0.8–25 J cm⁻²). Photothermal models based on Beer–Lambert equation using thermal diffusivity and absorption coefficient, energy balance, and heat transfer were presented to predict the ablation mechanisms. Micromachining of trenches was demonstrated at 7 J cm⁻² to demonstrate the potential of UV laser ablation. Results indicate that the ablation process is characterized by two well-defined threshold fluences: (a) decomposition threshold ~1 J cm⁻² and (b) melting threshold ~1.5 J cm⁻² for both polytypes. Contrary to the modeling expectations, the ablation rates were lower and did not increase rapidly with energy fluence. Four types of ablation mechanisms—chemical decomposition, vaporization, explosive boiling, and plasma shielding—either singly or in combination occur as a function of energy fluence. The predictions of photothermal models were not in good agreement with the experimental data implying that a complex interplay among various physical phenomena occurs during ablation. Micromachined trench exhibited ripple patterns, microcracks and recast layers, most of which could be eliminated by a subsequent chemical cleaning process. It is concluded that excimer laser ablation is an effective but slow material removal process for SiC wafers compared to other lasers such as 1064 nm Nd:YAG.     

Micro‐ and Nanopatterning of Functional Organic Monolayers on Oxide‐Free Silicon by Laser‐Induced Photothermal Desorption

The photothermal laser patterning of functional organic monolayers, prepared on oxide‐free hydrogen‐terminated silicon, and subsequent backfilling of the laser‐written lines with a second organic monolayer that differs in its terminal functionality, is described. Since the thermal monolayer decomposition process is highly nonlinear in the applied laser power density, subwavelength patterning of the organic monolayers is feasible. After photothermal laser patterning of hexadecenyl monolayers, the lines freed up by the laser are backfilled with functional acid fluoride monolayers. Coupling of cysteamine to the acid fluoride groups and subsequent attachment of Au nanoparticles allows easy characterization of the functional lines by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Depending on the laser power and writing speed, functional lines with widths between 1.1 μm and 250 nm can be created. In addition, trifluoroethyl‐terminated (TFE) monolayers are also patterned. Subsequently, the decomposed lines are backfilled with a nonfunctional hexadecenyl monolayer, the TFE stripes are converted into thiol stripes, and then finally covered with Au nanoparticles. By reducing the lateral distance between the laser lines, Au‐nanoparticle stripes with widths close to 100 nm are obtained. Finally, in view of the great potential of this type of monolayer in the field of biosensing, the ease of fabricating biofunctional patterns is demonstrated by covalent binding of fluorescently labeled oligo‐DNA to acid‐fluoride‐backfilled laser lines, which—as shown by fluorescence microscopy—is accessible for hybridization.     

Agglomeration of amorphous silicon film with high energy density excimer laser irradiation

In this paper, agglomeration phenomena of amorphous Si (α-Si) films due to high energy density excimer laser irradiation are systematically investigated. The agglomeration, which creates holes or breaks the continuous Si film up into spherical beads, is a type of serious damage. Therefore, it determines an upper energy limit for excimer laser crystallization. It is speculated that the agglomeration is caused by the boiling of molten Si. During this process, outbursts of heterogeneously nucleated vapor bubbles are promoted by the poor wetting property of molten silicon on the SiO₂ layer underneath. The onset of the agglomeration is defined by extrapolating the hole density as a function of the energy density of the laser pulse. A SiO₂ capping layer (CL) is introduced on top of the α-Si film to investigate its influence on the agglomeration. It is found that effects of the CL depend on its thickness. The CL with a thickness less than 300 nm can be used to suppress the agglomeration. A thin CL acts as a confining layer and puts a constraint on bubble burst, and hence suppresses the agglomeration.     

Single crystal-like Si patterns for photonic crystal color filters

A novel fabrication method for a two-dimensional photonic crystal color filter based on guided mode resonance is proposed. An amorphous silicon layer deposited through the low-temperature plasma enhanced chemical vapor deposition (PECVD) process is patterned into two-dimensional structures using low-cost nanoimprint lithography. It is then effectively crystallized using multi-shot excimer laser annealing at low energy. We have demonstrated analytically and experimentally that single crystal-like silicon patterns on a glass substrate can offer high-efficiency photonic crystal color filters for reflective display applications. The highly crystallized silicon patterning scheme presented here may be very attractive for a variety of devices requiring high carrier mobility and high optical efficiency.     

A carbon nanotube–enhanced SiC coating for the oxidation protection of C/C composite materials

A carbon nanotube–enhanced SiC (CNT–SiC) coating was deposited on C/C composites to improve the oxidation resistance of C/C. The CNT–SiC coating was prepared by direct growth of CNTs on C/C surface at 700 °C followed by deposition of SiC using chemical vapor deposition at 1150 °C for 1 h. SiC was deposited on the CNTs as well as the interface between CNTs and C/C, making CNTs strongly rooted on C/C surface. The final CNT–SiC coating consisted of two layers: the CNT–SiC layer and SiC layer. In comparison to the SiC coating, the CNT–SiC coating showed fewer cracks and a better oxidation resistance because the CNTs reduce the stress in the coating caused by the mismatch of the coefficient of thermal expansion between C/C and SiC.     

Silver diffusion and high-temperature lubrication mechanisms of YSZ–Ag–Mo based nanocomposite coatings

Yttria-stabilized zirconia (YSZ) nanocomposite coatings consisting of silver and molybdenum were produced by a hybrid process of filtered vacuum arc, magnetron sputtering and pulsed laser depositions for tribological investigations at different temperatures. The coatings with 24 at.% Ag and 10 at.% Mo contents showed a friction coefficient of 0.4 or less for all temperatures from 25 to 700 °C. The wear scar surfaces and coating cross-sections were studied using scanning electron, transmission electron, scanning transmission electron and focused ion beam microscopes, which also provided the information on chemical composition distributions of silver and molybdenum along with microstructure features. It was demonstrated that silver diffusion and coalescence on surfaces played an important part in the high-temperature lubrication mechanism of the YSZ–Ag–Mo coatings. Silver was found to be an effective lubricant at temperatures below 500 °C and its coalescence on the surface isolated molybdenum inside coatings from ambient oxygen. Lubricious oxides of molybdenum were formed and lubricated at temperatures above 500 °C when the silver was worn off the contact surface. For silver containment inside the coating at high temperatures, a multilayer architecture was built by inserting a TiN diffusion barrier layer in the composite coatings. Microscopic observations showed that this barrier layer prevented silver exit to the coating surface. At the same time, this enabled a subsequent lateral lubricant supply toward a wear scar location where the diffusion barrier layer was worn through and/or for a next thermal cycle. The multilayer coating maintained a friction coefficient of 0.4 or less for more than 25,000 cycles, while the monolithic coating lasted less than 5000 cycles. In addition, a TiN surface barrier layer with pinholes was deposited on the YSZ–Ag–Mo composite surface to control vertical silver diffusion. With this coating design, the coating wear lifetime was significantly increased beyond 50,000 cycles.     

Etching and printing of diffractive optical microstructures by a femtosecond excimer laser

Diffractive optics fabrication is performed by two complementary processing methods that rely on the photoablation of materials by ultrashort UV laser pulses. The spatially selective ablation of materials permits the direct microetching of high-quality surface-relief patterns. In addition, the direct, spatially selective transfer of the ablated material onto planar and nonplanar receiving substrates provides a complementary microprinting operation. The radiation from the ultrashort pulsed excimer laser results in superior quality at relatively low-energy density levels, owing to the short absorption length and minimal thermal-diffusion effects. Computer-generated holographic structures are produced by both modes of operation. Submicrometer features, including Bragg-type structures, are microprinted onto planar and high-curvature optical-fiber surfaces, demonstrating the unique ability of the schemes for complex microstructure and potentially nanostructure development.     

Gas-phase growth of diameter-controlled carbon nanotubes

We demonstrate gas-phase (aerosol) generation of diameter-controlled carbon nanotubes (CNTs) by employing size-controlled monodisperse nickel nanoparticles produced by the combination of pulsed laser ablation and electrostatic classification. The electrostatic classifier sorted agglomerated mono-area nickel particles, and then a subsequent heating process at ∼ 1200 °C created sintered single primary particles with very narrow size distribution. These isolated single primary particles were then sent to an aerosol reactor where free-flight CNTs were grown with acetylene and hydrogen mix at temperature of ∼ 750 °C. The resulting CNTs formed in this continuous gas-phase process were found to have a uniform diameter, which is commensurate with the diameter of the size-controlled catalytic nickel particles.     

Low energy O2 and N2O ion beam modification of polyimide for improving adhesive strength of Cu/PI in roll-to-roll process

To enhance the weak mechanical durability of directly deposited copper layers on polyimide (PI) film due to their poor adhesive strength, a continuous roll-to-roll process involving surface modification using a reactive ion beam irradiation and in-situ deposition process is studied. The polyimide film is modified by an ion source with a linear stationary plasma thruster (LSPT) in the vacuum roll-to-roll process. An O₂ ion beam, with beam energy of 214 eV and beam current density of 0.78 mA/cm², and N₂O ion beam, with 220 eV and 0.69 mA/cm², irradiate PI film in winding speed of 0.5 m/min. The surface energy increases from 38 mN/m for the pristine PI film to 80 mN/m after beam irradiation at an ion fluence of 3.5 × 10¹⁶ ions/s. After beam irradiation, a 10 nm thick tie layer and 200 nm thick copper layer are successively deposited by in-situ DC magnetron web coating. The peel strength of the copper layer on the PI film is enhanced from 0.4 kgf/cm without ion beam treatment to 0.71 kgf/cm after O₂ beam treatment and to 0.75 kgf/cm after N₂O beam treatment. This enhancement is closely related to the increase in the polar force originating from the formation of hydrophilic CO (carbonyl) groups on the modified PI surface.     

Fabrication of a Thermally Isolated and Pre-Amplified Transistor Module with Polyimide Micro-Wires for Cryogenic Detectors

We report a pre-amplifying junction field effect transistor (JFET) module on a chip for cryogenic applications such as bolometer and X-ray microcalorimeter. In order to maintain the optimum performance of the JFETs at 130 K, the module has built-in aluminum micro-heaters while the JFETs are thermally isolated from a heat sink. The thermal isolation is achieved by suspending a micromachined silicon support platform (6 μm thick) with polyimide wires. A layer of aluminum electrodes is patterned on top of the polyimide wires for electrical contacts and on top of the silicon platform for the heaters. This process involves reactive-ion-etching (RIE) of silicon and polyimide, patterning of aluminum electrodes over the polyimide, back side deep-reactive-ion-etching (DRIE) of silicon, and releasing of the modules. In this paper, we describe a micromachining process of the JFET modules on silicon-on-insulator (SOI) wafers.      

HIGH Tc SUPERCONDUCTING THIN FILM DEPOSITION BY LASER INDUCED FORWARD TRANSFER

We review in this paper the basic mechanisms and potential applications of the Laser Induced Forward Transfer (LIFT) for the rapid deposition and patterning in a clean environment, of high Tc superconducting thin films. A stoichiometric oxide superconductor compound is initially deposited, in a thin layer, on an optically transparent support. By irradiating, under vacuum or in air, this precoated layer with a strongly absorbed single laser pulse through the transparent support, the film is removed from its support to be transferred onto a selected target substrate, held in contact or close to the original film. The mechanisms for transferring YBaCuO and BiSrCaCuO thin films, with a pulsed UV excimer laser are described using a thermal melting model based on the resolution of the heat flow equation. The various possibilities given by the LIFT technique for patterning high Tc films (mask and direct patterning) are also examined.