Polymer microchips bonded by O2-plasma activation

This paper presents a fabrication of polymer microchips with homogeneous material technique due to surface treatment by plasma before sealing. UV laser photoablation was used for fast prototyping of microstructures, and oxygen plasma was used as a surface treatment for both the microfabricated substrate and the polymer cover. It was found that with an oxidative plasma treatment, successful bonding could be achieved without adhesive material between polymer sheets substantially below the glass transition temperature of the polymer. Homogeneous polyethylene terephthalate (PET) microstructures were characterized by scanning electron microscopy (SEM) and analyzed by X-ray photoelectron spectroscopy (XPS) surface analyses after different surface treatments. The electroosmotic flow characteristics including the velocity and the stability over 20 days have been tested and compared to composite channels, in which the cover presents a polyethylene (PE) adhesive layer. Capillary zone electrophoresis in both homogeneous and composite microanalytical devices were then performed and compared in order to evaluate the separation efficiency. In preliminary experiments, a plate height of 0.6 m has been obtained with homogenous microchannels. The surface analysis pointed out that the surface chemistry is of prime importance for the performance of microfluidic separation.

Selective light induced chemical vapour deposition of titanium dioxide thin films

Estelle Wagner

Light Induced Chemical Vapour Deposition (LICVD) of titanium dioxide thin films is studied in this work. It is shown that this technique enables to deposit locally and selectively a chosen crystalline phase with a precise controlled thickness at low substrate temperature, allowing even the use of polymer substrates. A home made LICVD reactor was set up, consisting of a main chamber in which the substrate was placed on a temperature controlled plate and could be irradiated perpendicularly through a window by a 250 ns long pulse XeCl excimer laser (308 nm) with a controlled fluence (energy per surface area per pulse). A liquid precursor (titanium tetra-isopropoxide) was brought by an oxygen carrier gas flow in the chamber and a nitrogen flow was added to prevent deposition on the window. The total pressure in the chamber was maintained at 10 mbar. Projection of a mask image on the substrate was realized. Titanium dioxide films could be deposited locally by this technique with a thickness ranging from few nanometers to several micrometers. Deposits were realized at substrate temperatures as low as room temperature and with fluences between 1 and 400 mJ/cm2. The deposited films were characterized by profilometry, Atomic Force Microscopy, optical microscopy, Scanning Electron Microscopy, Transmission Electron Microscopy, X-ray diffraction, Raman spectroscopy, X-ray Photoelectron Spectroscopy, UV-vis spectroscopy and ellipsometry. A detailed and systematic study of the influence of some selected process parameters (substrate temperature and irradiation dose principally) on the deposition rate and material properties was realized on glass and silicon substrates. An empirical equation of the growth rate as a function of the different experimental parameters was derived and was tested successfully to obtain a precise control of the deposited thickness (a precision better than 10 nm was demonstrated for films below 300 nm), with growth rates up to 300 nm/min. From this equation, a deposition mechanism involving both a photolytic reaction and a thermal contribution of the substrate temperature was proposed. The deposited material was shown to consist of TiO2 with a possible very low additional carbon contamination. Depending on the deposition conditions, amorphous, anatase or rutile material was deposited. One parameter explaining the variation of the crystalline state of the material was the variation of the laser induced temperature rise which was simulated theoretically in parallel. Surface temperature rises in the order of several hundreds of degrees were calculated during the laser pulse, varying with the substrate, the fluence and the film thickness. The optical properties of the deposited material vary in a correlated way with the crystalline state of the material, and high indexes of refraction (up to 2.6 at 633 nm) were measured. Selective deposition in the irradiated area was studied. Provided substrate temperature was kept below 150°C, no thermal deposition was observed, and deposits were strictly located in the irradiated area. The edge resolution (around 10 micrometers) was demonstrated to be due to the optical aberrations of the mask projection set up. No effect of substrate temperature and irradiation conditions on the resolution could be evidenced, but resolution decreased with increasing deposited thickness due to optical effects. Thanks to the low substrate temperature required for the deposition process, deposition on thermo- fragile substrates (such as polymers, in particular PMMA) was demonstrated. However, in the case of polymer substrates, the fluence had to be kept below 15 mJ/cm2 not to damage or ablate the polymers, resulting in very low growth rates (in the order of 10-3 nm/pulse). In these conditions, only amorphous films with about 10% of carbon contamination could be obtained. Additionally, films were shown to crack above a certain deposited thickness, which is attributed to thermal effects. As a matter of fact, calculations showed a high temperature rise up to 70°C of the polymer/oxide interface. Deposition on polymers coated with transparent conductive oxide was also demonstrated.

EPFL2003

Light trapping polymer-based coatings for cost effective flexible thin film photovoltaics

Marina Aymara González Lazo

Thin film silicon solar cells benefit from a lower fabrication cost than crystalline silicon cells, but they have a lower efficiency. The aim of this thesis was to explore the light-management capabilities of sub-micron polymer-based textures, both for the back reflector and for the front encapsulation of thin film silicon solar cells. The thin active layers of these devices require some form of photon path length enhancement to increase their efficiency. For this purpose, light trapping textures were replicated using transparent low shrinkage acrylate hyperbranched polymer nanocomposites. To enable low pressure replication of textures with enhanced mechanical performance, silica nanoparticles and silicon-based sol-gel precursors were combined to create novel low viscosity hybrid nanocomposite resins. Indeed, the viscosity of these hybrid suspensions was found to be one to two orders of magnitude lower than that of particulate suspensions with an equivalent silica loading. The hybrid resins were cured by combined UV polymerization and condensation, and the mechanical performance of the resulting nanocomposites was characterized in terms of their Vickers microhardness. The Vickers microhardness increased from 112 MPa for the unmodified polymer matrix to 190 MPa and 148 MPa for the hybrid nanocomposites and particulate nanocomposites, respectively, at 20 vol% silica, and reached as much as 287 MPa for the hybrid nanocomposites at 30 vol% silica. For the back reflector, light scattering (LS) textures in the form of random sub-micron pyramidal features were replicated in the nanocomposites using a nickel template and UV-nanoimprint lithography. The influence of nanoparticle content and pressure on the morphology and light scattering properties of the replicas was studied using scanning electron microscopy and optical analysis. The roughness and coherence length of the textures were similar to those of the template for all the compositions and process pressures investigated. After optimization of the dual-cure process, very high replication fidelity could be obtained in each case, leading to haze greater than 99 % over the whole of the visible light spectrum and very effective light scattering performance for a broad range of angles. A durable antireflective (AR) front encapsulation is also key to enhancing the photovoltaic performance of thin film silicon solar cells. The AR performance of hyperbranched polymer nanocomposite textures replicated from a moth eye pattern using UV-nanoimprint lithography was established both experimentally and through simulations. Optimum patterns were found on the basis of effective medium theory (EMT) to be arrays of paraboloids with a periodicity of 340 nm, which provided stable AR performance for aspect ratios in the range of 0.6 to 1.75. Good agreement was obtained between the simulated and measured optical behavior of such AR arrays, with a normal reflectance in the visible range of around 4 % when using a glass substrate. The simulations also predicted a reduction in the hemispherical reflectance from 15 % to 6 % for this texture. A hierarchical texture was replicated from a lotus leaf into the hyperbranched polymer modified with a perfluorinated acrylate, and the same material was also used to replicate the AR moth eye texture. In both cases, the replication fidelity was again found to be excellent and the textures exhibited improved hydrophobicity. [...]

EPFL2015

Poleable Nanoparticles as Fillers Towards Non-linear Optically Active Actuators

Yee Song Ko

A new type of poleable dielectric elastomer is introduced herein. The elastomer contains polymer nanoparticles with frozen molecular dipoles, which can be oriented at elevated temperatures in an electric field via poling. The aim is to provide a soft material with high, tunable optical properties suitable for actuator and flexible electronics applications. To that end poleable polymeric nanoparticles with high dipole concentrations and glass transition temperatures well above room temperature will be needed to be used as filler in an elastomer matrix. The synthesis and characterization of such particles is presented in this manuscript. Polyhydroxyethyl methacrylate (PHEMA) nanoparticles were synthesized using miniemulsion polymerization. The particles were loaded with 4-[ ethyl (2-hydroxyethyl) amino]-4-nitrobenzene, usually called Disperse Red 1 (DR1), which has a large dipole moment (mu = 7.5 - 9.5 D). (1) The maximum dipole loadings is limited by the solubility of the dipole in the monomer solutions prior to polymerization. All samples show a glass transition temperature around 95 degrees C. Secondary electron microscopy (SEM) revealed spherical particles, the size of which was confirmed by dynamic light scattering (DLS) measurements. A composite was prepared by dispersing the particles in polydimethyl siloxane (PDMS).