Production of Nanomaterials by Pulsed Laser Ablation

Nanotechnology has been predicted to change many aspects of our everyday life and revolutionize the way we produce materials. The remarkable size-tunable properties of nanomaterials make them a hot research topic with far-reaching applications ranging from quantum computers to cures for cancer. To achieve these ambitious visions, new production methods need to be developed. In this thesis the production of nanomaterials by pulsed laser ablation is investigated. This work was initially motivated by an interest to test recently developed high repetition rate fibre lasers in pulsed laser deposition (PLD) and pulsed laser ablation in liquids (PLAL). In this work PLD was used to deposit thin films, nanoparticles and high surface area structures. The high repetition rate was observed to have important implications for the quality of the deposited films and the surfaces of the evaporated targets. Nanoparticles produced by conventional chemical synthesis techniques often include unwanted residues from the reactants. These residues can be toxic and detrimental for applications. Nanoparticle production by PLAL has been shown to be a method capable of producing pure nanoparticles directly from a wide variety of bulk materials and compounds. In this work a single-step PLAL process for production of luminescent GaAs-nano-particles and silica-coated gold nanoparticles was developed

Mikroskopiakonferenssi Scandem 2022

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Ion Beam Assisted E-Beam Deposited TiN Microelectrodes—Applied to Neuronal Cell Culture Medium Evaluation

Microelectrode material and cell culture medium have significant roles in the signal-to-noise ratio and cell well-being in in vitro electrophysiological studies. Here, we report an ion beam assisted e-beam deposition (IBAD) based process as an alternative titanium nitride (TiN) deposition method for sputtering in the fabrication of state-of-the-art TiN microelectrode arrays (MEAs). The effects of evaporation and nitrogen flow rates were evaluated while developing the IBAD TiN deposition process. Moreover, the produced IBAD TiN microelectrodes were characterized by impedance, charge transfer capacity (CTC) and noise measurements for electrical properties, AFM and SEM for topological imaging, and EDS for material composition. The impedance (at 1 kHz) of brand new 30 μm IBAD TiN microelectrodes was found to be double but still below 100 kΩ compared with commercial reference MEAs with sputtered TiN microelectrodes of the same size. On the contrary, the noise level of IBAD TiN MEAs was lower compared with that of commercial sputtered TiN MEAs in equal conditions. In CTC IBAD TiN electrodes (3.3 mC/cm2) also outperformed the sputtered counterparts (2.0 mC/cm2). To verify the suitability of IBAD TiN microelectrodes for cell measurements, human pluripotent stem cell (hPSC)-derived neuronal networks were cultured on IBAD TiN MEAs and commercial sputtered TiN MEAs in two different media: neural differentiation medium (NDM) and BrainPhys (BPH). The effect of cell culture media to hPSC derived neuronal networks was evaluated to gain more stable and more active networks. Higher spontaneous activity levels were measured from the neuronal networks cultured in BPH compared with those in NDM in both MEA types. However, BPH caused more problems in cell survival in long-term cultures by inducing neuronal network retraction and clump formation after 1–2 weeks. In addition, BPH was found to corrode the Si3N4 insulator layer more than NDM medium. The developed IBAD TiN process gives MEA manufacturers more choices to choose which method to use to deposit TiN electrodes and the medium evaluation results remind that not only electrode material but also insulator layer and cell culturing medium have crucial role in successful long term MEA measurements

Uncovering exceptional micro-scale plasticity accommodation mechanisms in amorphous aluminum oxide through experimental and simulation results

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Halogen-bonded shape memory polymers

Halogen bonding (XB), a non-covalent interaction between an electron-deficient halogen atom and a Lewis base, is widely adopted in organic synthesis and supramolecular crystal engineering. However, the roadmap towards materials applications is hindered by the challenges in harnessing this relatively weak intermolecular interaction to devise human-commanded stimuli-responsive soft materials. Here, we report a liquid crystalline network comprising permanent covalent crosslinks and dynamic halogen bond crosslinks, which possess reversible thermo-responsive shape memory behaviour. Our findings suggest that I···N halogen bond, a paradigmatic motif in crystal engineering studies, enables temporary shape fixation at room temperature and subsequent shape recovery in response to human body temperature. We demonstrate versatile shape programming of the halogen-bonded polymer networks through human-hand operation and propose a micro-robotic injection model for complex 1D to 3D shape morphing in aqueous media at 37 °C. Through systematic structure-property-performance studies, we show the necessity of the I···N crosslinks in driving the shape memory effect. The halogen-bonded shape memory polymers expand the toolbox for the preparation of smart supramolecular constructs with tailored mechanical properties and thermoresponsive behaviour, for the needs of, e.g., future medical devices.publishedVersionPeer reviewe

Effect of Partial Crystallization on the Structural and Luminescence Properties of Er3+-Doped Phosphate Glasses

Er-doped phosphate glass ceramics were fabricated by melt-quenching technique followed by a heat treatment. The effect of the crystallization on the structural and luminescence properties of phosphate glasses containing Al2O3, TiO2, and ZnO was investigated. Themorphological and structural properties of the glass ceramics were characterized by Field Emission-Scanning Electron Microscopy (FE-SEM), X-ray Diffraction (XRD), and micro-Raman spectroscopy. Additionally, the luminescence spectra and the lifetime values were measured in order to study the influence of the crystallization on the spectroscopic properties of the glasses. The volume ratio between the crystal and the glassy phases increased along with the duration of the heat treatment. The crystallization of the glass ceramics was confirmed by the presence of sharp peaks in the XRD patterns and different crystal phases were identified depending on the glass composition. Sr(PO3)2 crystals were found to precipitate in all the investigated glasses. As evidenced by the spectroscopic properties, the site of the Er3+ ions was not strongly affected by the heat treatment except for the fully crystallized glass ceramic which does not contain Al2O3, TiO2, and ZnO. An increase of the lifetime was also observed after the heat treatment of this glass. Therefore, we suspect that the Er3+ ions are incorporated in the precipitated crystals only in this glass ceramic

Exceptional Microscale Plasticity in Amorphous Aluminum Oxide at Room Temperature

Oxide glasses are an elementary group of materials in modern society, but brittleness limits their wider usability at room temperature. As an exception to the rule, amorphous aluminum oxide (a-Al2O3) is a rare diatomic glassy material exhibiting significant nanoscale plasticity at room temperature. Here, it is shown experimentally that the room temperature plasticity of a-Al2O3 extends to the microscale and high strain rates using in situ micropillar compression. All tested a-Al2O3 micropillars deform without fracture at up to 50% strain via a combined mechanism of viscous creep and shear band slip propagation. Large-scale molecular dynamics simulations align with the main experimental observations and verify the plasticity mechanism at the atomic scale. The experimental strain rates reach magnitudes typical for impact loading scenarios, such as hammer forging, with strain rates up to the order of 1 000 s−1, and the total a-Al2O3 sample volume exhibiting significant low-temperature plasticity without fracture is expanded by 5 orders of magnitude from previous observations. The discovery is consistent with the theoretical prediction that the plasticity observed in a-Al2O3 can extend to macroscopic bulk scale and suggests that amorphous oxides show significant potential to be used as light, high-strength, and damage-tolerant engineering materials.Peer reviewe

Automated solvent vapor annealing with nanometer scale control of film swelling for block copolymer thin films

Molecular self-assembly of block copolymers has been pursued as a next generation high-resolution, low-cost lithography technique. Solvent vapor annealing is a promising way of achieving self-assembled patterns from polymers with high interaction parameters, χ, or high molecular weights. Compared to thermal annealing, the assembly in a solvated state can be much faster, but the film swelling process is typically challenging to control and reproduce. We report the design and implementation of an automated solvent annealing system that addresses these issues. In this system the film swelling is controlled via local heating or cooling, which enables exceptionally fast and precise modulation of the swelling. The swelling of the polymer films follows preprogrammed annealing profiles with the help of a feedback loop that compares and tunes the film thickness with respect to the set point. The system therefore enables complex annealing profiles such as rapid cyclic swelling and deswelling. We show that the orientation of the pattern morphology and the amount of lattice defects are influenced by the used annealing profile. We demonstrate that optimized profiles significantly shorten the annealing time (<15 min) of high-χ and high-molecular weight poly(styrene-b-2-vinylpyridine).publishedVersionPeer reviewe

Unexpected role of hyaluronic acid in trafficking siRNA across cellular barrier: First biomimetic, anionic, non-viral transfection method

Circulating nucleic acids, such as short interfering RNA (siRNA), regulate many biological processes; however, the mechanism by which these molecules enter the cell is poorly understood. The role of extracellular‐matrix‐derived polymers in binding siRNAs and trafficking them across the plasma membrane is reported. Thermal melting, dynamic light scattering, scanning electron microscopy, and computational analysis indicate that hyaluronic acid can stabilize siRNA via hydrogen bonding and Van der Waals interactions. This stabilization facilitated HA size‐ and concentration‐dependent gene silencing in a CD44‐positive human osteosarcoma cell line (MG‐63) and in human mesenchymal stromal cells (hMSCs). This native HA‐based siRNA transfection represents the first report on an anionic, non‐viral delivery method that resulted in approximately 60 % gene knockdown in both cell types tested, which correlated with a reduction in translation levels.acceptedVersionPeer reviewe

Better understanding of the role of SiO2, P2O5 and Al2O3 on the spectroscopic properties of Yb 3+ doped silica sol-gel glasses

Yb 3+ doped silica sol-gel glass powders were prepared with different concentrations of SiO2, Al2O3 and P2O5 in order to understand the impact of the glass composition on the Yb 3+ emission properties. In this paper, we clearly show that not only the Al/P ratio but also the SiO2 content have an impact on the Yb 3+ spectroscopic properties. Our results provide new insight on the real impact of the composition on the spectroscopic properties of Yb 3+ doped sol-gels: we demonstrate that an increase in the Al2O3 content at the expense of P2O5 leads to an increase in the intensity of the emission at 1000nm of the Yb 3+ ions whereas an increase in the SiO2 content decreases it. We clearly showed that the inexpensive sol-gel approach can be easily used when investigating new Yb 3+ doped silica glasses