Functional polymers by two-photon 3D lithography

In the presented work, two-photon 3D lithography and selective single-photon photopolymerization in a prefabricated polydimethylsiloxane matrix is presented as an approach with potential applicability of waveguide writing in 3D by two-photon polymerization.Photopolymers based on acrylate chemistry were used in order to evaluate the optical capabilities of the available two-photon system. Several photoinitiators, tailored for two-photon absorption, were tested in a mixture of trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate. Best results were obtained with a recently synthesized diynone-based photoinitiator. Feature resolutions in the range of 300 nm were achieved. Due to the cross-conjugated nature of that donor-π-acceptor-π-donor system a high two-photon absorption activity was achieved. Therefore, a resin mixture containing only 0.025 wt% of photoinitiator was practical for structuring by two-photon polymerization. The required initiator content was therefore a factor of 100 lower than in traditional one-photon lithography.The aim of the second part of this work was to fabricate optical waveguides by selectively irradiating a polymer network, which was swollen by a monomer. The monomer was polymerized by conventional single-photon polymerization and the uncured monomer was removed by evaporation at elevated temperatures. This treatment leads to a local change in refractive index. Refractive index changes in the range of Δn = 0.01 (Δn/n = 0.7%) were achieved, which is sufficient for structuring waveguides for optoelectronic applications.     

Pattern generation using axicon lens beam shaping in two-photon polymerisation

The fabrication of three-dimensional microstructures by two-photon polymerisation has been widely reported as a viable route to the development of photonic crystals, rotors, bridges and other complex artefacts requiring nanoscale resolution. Conventionally, single point serial writing is used to write the structures but recently multipoint beam delivery using beam division optics has been reported as a method of introducing parallel processing. In this paper we present an alternative and novel approach using an axicon lens to give profiled beam delivery. This enables complete three-dimensional annular structure fabrication without the use of scanning stages. In addition, the concept of axicon delivery is developed further to investigate three-dimensional structure as a function of axicon geometry.A Ti:sapphire laser, with wavelength 795 nm, 80 MHz repetition rate, 100 fs pulse duration and an average power of 700 mW, was used to initiate two-photon polymerisation. The axicon was used, in combination with a 100× microscope objective, to form representative three-dimensional structures based on the annular cell with varying diameter. The structures were written in a Zr-loaded resin prepared on a glass substrate using dip coating deposition of a Zr/PMMA hybrid prepared by the sol-gel method. Annuli with diameters up to 50 μm were characterised in terms of topography and surface roughness using SEM and Zygo interferometer. The writing technique was also extended to fabrication of stacked structures.     

Manipulation of organic “needles” using an STM operated under SEM control

Nano-sized P4P (para-quaterphenylene) organic crystallites grown on a gold substrate were removed and redeposited using the tip of an STM. The controlled lift-off of the needle-shaped crystallites was imaged by a simultaneously operated SEM. The forces exerted by the metal STM tip on the nano-crystal during this nano-manipulation process could be determined by monitoring the deflection of the STM tip. After the lift-off process the former contact area was imaged using the STM. These STM micrographs clearly demonstrate that the region between the needles is covered by a P4P layer with a thickness of at least 3 nm.     

Sonication-assisted layer-by-layer deposition of gold nanoparticles for highly conductive gold patterns

Sonication-assisted layer-by-layer (LBL) deposition of gold nanoparticles (GNPs) was carried out in an attempt to prepare highly conductive gold patterns on polyimide substrates. First, sonication time was optimized with GNPs (12.8 nm) whose size was large enough to be analyzed by FE-SEM in order to evaluate the surface coverage. Next, multilayer formation (4, 8 and 12 layer) was confirmed using ethanedithiol (EDT) as linker molecules under optimized conditions by measuring their UV absorption, near-IR (NIR) transmittance, thickness, and electrical conductivity. Finally, 20-layer films using small GNPs (2.5 nm) were prepared with or without patterning, followed by sintering at 150 °C for 1 h, which provided clean gold patterns with high electrical conductivity (2.5 × 10⁵ Ω⁻¹ cm⁻¹).     

Fabrication of grating structures by simultaneous multi-spot fs laser writing

Two-photon polymerisation is an established technique for the fabrication of three-dimensional microstructures. To date structures have mostly been developed using single beam serial writing. A novel approach to simultaneous multi-spot two-photon polymerisation, that uses a SiO₂ on glass Fraunhofer diffractive optical element to generate an array of beamlets, is described. A Ti:sapphire laser, with wavelength 790 nm, 80 MHz repetition rate, 100 fs pulse duration and an average power of 25 mW, was used to initiate two-photon polymerisation. The DOE, in combination with a high power microscope objective, efficiently transforms the laser beam into a linear array of four spots of equal intensity. The fabrication of a periodic transmission grating, using parallel processing with these four spots, is shown. The grating was written in a Zr-loaded resin prepared on a glass substrate using dip coating deposition of a Zr/PMMA hybrid prepared by the sol-gel method. The operation of the diffractive element and the performance of the diffraction grating are also discussed.     

Very high coercivities of top-layer diffusion Au/FePt thin films

The Au/FePt samples were prepared by depositing a gold cap layer at room temperature onto a fully ordered FePt layer, followed by an annealing at 800 °C for the purpose of interlayer diffusion. After the deposition of the gold layer and the high-temperature annealing, the gold atoms do not dissolve into the FePt Ll₀ lattice. Compared with the continuous FePt film, the TEM photos of the bilayer Au(60 nm)/FePt(60 nm) show a granular structure with FePt particles embedded in Au matrix. The coercivity of Au(60 nm)/FePt(60 nm) sample is 23.5 kOe, which is 85% larger than that of the FePt film without Au top layer. The enhancement in coercivity can be attributed to the formation of isolated structure of FePt ordered phase.     

Normal incidence X-ray standing wave analysis of thin gold films

Normal incidence X-ray standing wave (NIXSW) analysis has been successfully performed on epitaxial gold films on mica substrates using reflection from the (1 1 1) planes parallel to the surface. We show that NIXSW can be used to monitor the decrease in order within the gold film caused by annealing, and the position of sulfur within a monolayer of methyl thiolate (CH₃S-) on the surface. The Au-S layer spacing was found to be 2.54 ± 0.05 Å, in close agreement with previous work on a single crystal system.     

Desorption and photopolymerization behavior of mixed and multilayered styrene-pyrrole nanofilms

The molecular arrangement and polymerization of adsorbed styrene-pyrrole films were explored using two different dosing schemes: simultaneous dosing to form an intimately mixed film of the two monomers and sequential dosing to form films with distinct layers of styrene and pyrrole. It was found that the desorption of pyrrole was delayed until 175 K when either simultaneously dosed with styrene or in the presence of an overlying styrene layer, whereas it normally desorbs at 165 K when dosed alone. No such effects were observed with styrene in any dosing configuration. The polymerization rate of pyrrole was unaffected in the films when present as the top layer and was observed to decrease by 50% when beneath a styrene layer. Moreover, the rate of polymerization increased by two orders of magnitude in the case of the intimately mixed film. The rate of styrene polymerization was not found to change in any of the explored geometries. These effects are explained by considering the proximity of the components and the potential for screening UV radiation based on their molecular structure.     

A new imaging method for gold-surface adsorbates based on anomalous reflection

A new imaging method is proposed for ultrathin films with a thickness of a few nanometers, based on the anomalous reflection (AR) of gold. In the AR effect, the reflectivity fairly decreases for blue or purple light (380 nm < λ < 480 nm) with the existence of a transparent dielectric layer at a gold surface. Thus, a thin gold film can be used as an imaging platform. Clear AR images are obtained for a microarray of protein (avidin) spots of diameter 120 μm with gaps of size 50 μm between the spots (36 spots/mm²). The resolution of the AR imaging is governed solely by the illumination spot size. AR imaging is a promising technique for high throughput analysis of biomolecular detection in a microarray format.     

Selective gold nano-patterning on flexible polymer substrate via concurrent nanoimprinting and nanotransfer printing

We report a simple technique of selective gold nano-patterning on non-planar polycarbonate substrate by combining nanoimprinting and gold nanotransfer printing techniques in a single concurrent nano-patterning process: thermal nanoimprinting directly patterns a MPTMS (3-mercaptopropyl trimethoxysilane)-coated polycarbonate sheet to form the non-planar nanostructures using a gold-film deposited mold. Simultaneously, the gold-film from the mold is selectively transfer-printed either onto the protrusion or the base of the imprinted non-planar structures. This high nano-patterning selectivity is achieved due to a combined effect of a thiol-terminated MPTMS-gold surface chemistry, more importantly, aided by a surface area dependent differential work of adhesion. We show the high delineation of the patterned gold on the non-planar polycarbonate substrate of various geometries such as pillars, dimples, and gratings, down to nano-scale resolution (130 nm) as well as over micro-scale resolution (10 μm), thus demonstrating that this can be a generic metal patterning technique. Using this technique, we fabricate a metal nanowire grid polarizer to demonstrate a potential device application. The main advantage of this technique lies in its inherent self-aligned process that simplifies selective Au nano-patterning on non-planar polymer surfaces, which is otherwise difficult to be obtained using conventional patterning techniques.     

Thermally assisted writing for perpendicular MRAM

Spin valves composed of TbCo/CoFe/Cu/CoFe/TbFeCo were fabricated with perpendicular magnetization and GMR ratios of 4.5%. The (TbCo/CoFe) layers and (CoFe/TbFeCo) layers are referred to the free and the pinned layers, respectively. The compositions of two layers were chosen to have a lower Curie temperature (130 °C) but higher coercivity (13.2 kOe) of the free layer at room temperature than those of the pinned layer; therefore, the free layer is quite stable at room temperature but its magnetization can be easily switched at a relatively low temperature. Spin valves were patterned into 100-μm-wide cells and their coercivity was reduced with increasing writing current due to the temperature rise by current-heating. When the current density of the writing current was increased to 2.1×10⁶ A/cm², the required switching field for the free layer was only 10 Oe.     

Direct observation of slow morphological transformations and wetting behavior of pulsed laser deposited sub-monolayer gold on (0 0 0 1) sapphire in atmosphere

Using high-resolution atomic force microscope we observed in ambient atmosphere the slow morphological transitions of the incipient adlayer of gold grown on (0 0 0 1) sapphire substrate by pulsed laser deposition. The equivalent average uniform thickness of the gold deposition was about 0.55 Å, which is about one-fourth of its monolayer. A dynamic simulation revealed that about 10% of the gold was implanted into the substrate up to the depth of about 3.3 nm and the top monolayer of the sapphire surface was almost completely depleted of oxygen atoms due to the preferential sputtering by the plume particles. The gold adlayer transformed into a labile phase which enhanced the surface roughness and had a preferred orientation of a wavy structure during 24 h of the deposition. The auto-correlation function of this wavy structure in labile metastable phase revealed two-fold symmetry and provided a preferential size of about 4 nm (peak to peak) with a mean separation of 8 nm. At the end of about 6 days this phase was found to completely transform into an apparently de-wetted phase of beads with average in-plane diameter of ∼20 nm and height of ∼7 nm having large size distribution. Each bead was seen to have coating of a concentric corona layer, which might be that of the condensed moisture or other gaseous species from atmosphere because subjecting these samples to vacuum removed this layer. These observations shed light on the dynamics of the pulsed laser deposited metastable gold adlayer in the incipient stage of its growth on sapphire and their wetting or de-wetting mechanisms in ambient atmosphere.     

Embedded dots inside glass for optical film using UV laser of ultrafast laser pulse

Microstructures are usually fabricated on the surface of optical sheets to improve the optical characteristics. In this study, a new fabrication process with UV (ultraviolet) laser direct writing method is developed to embed microstructures inside the glass. Then the optical properties of glass such as reflection and refraction indexes can be modified. Single- and multi-layer microstructures are designed and embedded inside glass substrate to modify the optical characteristics. Both luminance and uniformity can be controlled with the embedded microstructures. Thus, the glass with inside pattern can be used as a light guide plate to increase optical performance. First, an optical commercial software, FRED, is applied to design the microstructure configuration. Then, UV laser direct writing with output power 2.5-2.6 W, repetition rate 30 kHz, wave length: 355 nm, and pulse duration 15 ns is used to fabricate the microstructures inside the glass. The effect of dot pattern in the glass such as the dot pitch, the layer gap, and the number of layer on the optical performance is discussed. Machining capacity of UV laser ranges from micron to submicrometer; hence with this ultrafast laser pulse, objectives of various dimensions such as dot, line width, and layers can be easily embedded in the glass by one simple process. In addition, the embedded microstructures can be made with less contamination. Finally, the optical performance of the glasses with various configurations is measured using a Spectra Colorometer (Photo Research PR650) and compared with the simulated results.     

Patterning thin metallic film via laser structured weakly bound template

A weakly bound buffer material is structured on a surface by interfering low power laser beams, as a template for patterning metallic thin films deposited on top. The excess buffer material and metal layer are subsequently removed by a second uniform laser pulse. This laser pre-structured buffer layer assisted patterning procedure is demonstrated for gold layer forming a grating on a single crystal Ru(1 0 0) under UHV conditions, using Xe as the buffer material. Millimeters long, submicron (0.65 μm) wide wires can be obtained using laser wavelength of 1.064 μm with sharp edges of less than 30 nm, as determined by AFM. This method provides an all-in-vacuum metallic film patterning procedure at the submicron range, with the potential to be developed down to the nanometer scale upon decreasing the patterning laser wavelength down to the UV range.     

Fabrication and adhesion performance of gold conductive patterns on silicon substrate by laser sintering

Laser sintering of gold-microparticle ink was examined in this study. Laser-sintered gold conductive patterns were characterized by using scanning electron microscope (SEM), energy-dispersive spectrometer (EDS), cross-cut tape test and destructive bond wire pull tests. The effects of laser power on microstructure and adhesion of gold conductive patterns were investigated. It was found that the microstructure of gold conductive patterns became denser with increase of laser power. The gold conductive patterns treated with laser power of 2 W showed poor adhesiveness of 2B in accordance with ASTM D3359-08. The adhesion level of gold conductive patterns increased to 5B by elevating laser power to 8 W. The adhesion mechanism of gold conductive patterns on silicon substrate was discussed and wire bonding test was also performed on gold conductive patterns. Wire breakage took place at the practical pull strength of around 5 gf.     

Adsorption of carbon monoxide Au/Pd(1 0 0) alloys in ultrahigh vacuum: Identification of adsorption sites

The adsorption of carbon monoxide is studied on Au/Pd(1 0 0) alloys by means of reflection-absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD). The alloy was formed by adsorbing a four-monolayer thick gold film on a Pd(1 0 0) substrate and by heating to various temperatures to form alloys with a range of palladium coverages. The alloy was characterized using X-ray photoelectron spectroscopy and the composition of the outermost layer measured using low-energy ion scattering spectroscopy. CO adsorbs on palladium bridge sites only for palladium coverages greater than 0.5 monolayers (ML) suggesting that next-nearest neighbor sites are preferentially populated by palladium atoms. CO adsorbs on atop palladium sites and desorbs at ∼350 K corresponding to a desorption activation energy of ∼117 kJ/mol. However, at lower palladium coverages, these sites are not occupied and CO desorption states are detected 170 and 112 K corresponding to desorption activation energies of ∼53 kJ/mol and ∼35 kJ/mol, respectively, for these states. It is suggested that these states are due to a restructuring of the surface to form low-coordination gold sites that obscure the atop palladium site.     

Patterning of nanoparticulate transparent conductive ITO films using UV light irradiation and UV laser beam writing

Indium tin oxide (ITO) thin film is one of the most widely used as transparent conductive electrodes in all forms of flat panel display (FPD) and microelectronic devices. Suspension of already crystalline conductive ITO nanoparticles fully dispersed in alcohol was spun, after modifying with coupling agent, on glass substrates. The low cost, simple and versatile traditional photolithography process without complication of the photoresist layer was used for patterning ITO films. Using of UV light irradiation through mask and direct UV laser beam writing resulted in an accurate linear, sharp edge and very smooth patterns. Irradiated ITO film showed a high transparency (∼85%) in the visible region. The electrical sheet resistance decrease with increasing time of exposure to UV light and UV laser. Only 5 min UV light irradiation is enough to decrease the electrical sheet resistance down to 5 kΩ□.     

Evaluating the surface density and heterogeneity of a dithiobis (succinimidylpropionate) self-assembled monolayer on gold and its coupling with DNA embedded within a matrix

The homogeneity of a self-assembled monolayer (SAM) on a surface is an important parameter which affects the ability of a SAM to fulfill its intended function. As an example, SAMs formed from octanethiols can form an impermeable surface, while SAMs based on a bifunctional coupling reagent can form a surface with uniform reactivity. Exposure of gold nanoparticles or gold surfaces to solutions of dithiobis (succinimidylpropionate) (DSP) gives rise to a surface which can react with DNA. Atomic force microscopy, UV-vis and gel electrophoresis experiments indicate that a self-assembled monolayer of DSP on gold nanoparticles can attenuate aggregation, inhibit the “lying down” of covalently-bound single-stranded (ss) DNA and promote more efficient hybridization. The determination of the point of aggregation after reacting DSP with colloidal gold yields 2.86 × 10⁻¹⁰ mol/cm² or 42% of the value determined from molecular modeling. Cyclic voltammetry experiments validate that DSP on a gold quartz crystal (6.3 × 10⁻¹⁰ mol/cm²) forms a fairly uniform SAM that is within 94% of maximum coverage when compared with results obtained from molecular modeling (6.67 × 10⁻¹⁰ mol/cm²). Surface plasmon resonance experiments indicate that the reaction of a DSP coated gold surface with (ss) DNA yields 2.4 × 10⁻¹² mol/cm² or reaction with about 1% of the available surface area. Subsequent reactions of the DSP surface with the filler, n-boc-1,4-phenylene diamine (n-boc), yield a total surface coverage of 1.8 × 10⁻¹¹ mol/cm². The surrounded (ss) DNA yields a surface with 97% hybridization efficiency toward the complement.     

Hydrophobic modification of wood via surface-initiated ARGET ATRP of MMA

To convert the hydrophilic surface of wood into a hydrophobic surface, the present study investigated activators regenerated by electron transfer for atom transfer radical polymerization (ARGET ATRP) as a method of grafting methyl methacrylate (MMA) onto the wood surface. The wood treated with 2-bromoisobutyryl bromide and with the subsequently attached MMA via ARGET ATRP under different polymerization times (2 h, 4 h, 6 h, 8 h) were examined using scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. All the analyses confirmed that PMMA had been grafted onto the wood surface. Water contact angle measurement proved that the covering layer of PMMA on wood made the surface hydrophobic. Polymerization time had a positive influence on the contact angle value and higher contact angle can be produced with the prolongation of the polymerization time. When the reaction time was extended to 8 h, the contact angle of treated wood surface reached 130° in the beginning, and remained at 116° after 60 s. The ARGET ATRP method may raise an alteration on the wood surface modification.     

Nonlinear optics of nontoxic nanomaterials

We studied the linear and nonlinear optical properties of halloysite nanotubes using Z-scan technique. Halloysite is alumina silicate clay rolled into 50 nm diameter hollow cylinders, where the silica layer is at the outer surface of the tube and alumina layer is in the inner surface. Optical absorption spectra show an absorption peak around 600 nm. Open aperture Z-scan measurements using 3 ns laser pulses at 532 nm reveal two-photon induced absorption. The closed aperture Z-scan indicates a positive nonlinear refractive index. As these nanotubes are nontoxic and biocompatible, they have advantages over conventional carbon nanotubes for biomedical applications.