Patrick J. McNally

Activation energy for CaCO₃ calcination reaction was reduced using Ca₂Fe₂O₅ additives which improved the thermochemical cycling capacity of limestone waste.

During the pulsed laser ablation of metals, as well as other materials, the development of a plasma plume close to the ablated surface leads to the emission of radio frequency energy. In this paper, we describe a process for analysing the received radio frequency power (RFP) for an aluminium (Al) surface ablation process in atmosphere using picosecond laser pulses at a wavelength of 1064 nm. The analysis of the RFP was carried out on two sets of experiments, where two parameters of the laser (repetition rate of laser (RRL) and power of laser (PL)) were varied while other parameters remained constant. In addition to the RFP measurement during the laser processing, the spatter area (SA), which is defined in this paper, and the depth of the ablated hole were measured post-process using a 3D microscope. It was observed that there is a direct relationship between (RFP)² and SA. Accordingly, an appropriate RF calibration was performed, which leads to the definition of a quantity called the RF regulation % (RFR%). By comparing the RFR and PL/RRL variations, to which the laser beam fluence is proportional in these experiments, a diagnostic process (i.e., flowchart) for real-time depth evaluation was proposed and experimentally confirmed. This diagnostic process can indicate if the depth of the laser ablated crater is less than or exceeds a predetermined depth, which in this study was set to 15 µm. It is also demonstrated that the SA variation can be estimated in real-time by analysing the received RF power and, secondly, the depth of ablation can be measured in real time using a combination of information from the received RF power and laser parameters.

Enabling the carbonation reaction of Limestone waste by using CaZrO₃ nanoadditives.

In this report, a novel non-contact, non-invasive methodology for near and quasi real-time measurement of the structuring of metal surfaces using pulsed laser ablation is described. This methodology is based on the use of a multi-messenger data approach using data from Optical Emission Spectroscopy (OES) and Radio Emission Spectroscopy (RES) in parallel. In this research, radio frequency (RF) emission (in the range of 100–400 MHz) and optical emission (200–900 nm) were investigated and acquired in real-time. The RES and OES data were post-processed and visualized using heat maps, and, because of the large data sets acquired particularly using in RES, Principal Component Analysis (PCA) statistics were used for data analysis. A comparison between in-process RES-OES data and post-process 3D images of the different ablated holes generated by a picosecond laser with different powers (1.39 W, 1.018 W, and 0.625 W) on aluminum (Al) and copper (Cu) was performed. The real-time time-series data acquired using the Radio and Optical Emission Spectroscopy technique correlate well with post-process 3D microscopic images. The capability of RES-OES as an in operando near real-time diagnostic for the analysis of changes of ablation quality (cleanliness and symmetry), and morphology and aspect ratios (including the diameter of ablated holes) in the process was confirmed by PCA analysis and heat map visualization. This technique holds great promise for in-process quality detection in metal micromachining and laser-metal base manufacturing.

X-ray diffraction imaging was used to monitor the local strains that developed around individual n–p–n bipolar transistors within fully encapsulated packages under conditions of extremely high forward bias to simulate accelerated ageing. Die warpage associated with the packaging was observed to relax systematically as the polymer became viscous due to the temperature rise associated with the dissipation of heat in the transistor. The direct image size and intensity from the individual transistors were interpreted in terms of a model in which local thermal expansion is treated as a cylindrical inclusion of distorted material, contrast arising principally from lattice tilt. The extension of the thermal strain image along the emitter with increasing power dissipation was ascribed to the effect of current crowding in the emitter region. Weaker large-area contrast associated with the base–collector region was interpreted as arising from the smaller change in effective misorientation at the high X-ray energy of thermal lattice dilation in the base region.

Calcium carbonate (CaCO 3 ) is considered an ideal candidate for large scale energy storage systems due to its high energy density, high operating temperature and low cost. Its degrading performance over consecutive energy storage/release cycles is the main inhibiting factor from utilising such material as a high-temperature thermal battery for concentrated solar power (CSP) systems. In this study, silicon carbide (SiC) was added to calcium carbonate in three different weight concentrations (5, 10 and 20 wt% of SiC) as to improve the cycling stability of CaCO 3 over 40 cycles. SiC is an excellent additive since it is a chemically inert ceramic which possesses high heat conductivity, oxidation resistance, and temperature stability. Most importantly it does not chemically react with CaCO 3 upon cycling to form a ternary oxide, retaining the initial CaCO 3 energy storage density. The system which demonstrated the greatest improvement in cycling efficiency utilised 5 wt% SiC, which increased the cycling performance of pure CaCO 3 by a factor of 1.32. In order to further enhance the performance of this system, 300 and 100 nm polystyrene (PS) spheres were added to the SiC/CaCO 3 mixture respectively. The PS spheres were then removed by thermal treatment, creating a porous SiC/CaCO 3 structure with higher specific surface area in comparison to their bulk counterpart. Both porous mixtures showed an increase in their cycling stability for the first 20 cycles in relation to the bulk sample, allowing the CO 2 gas to travel through their porous structure, and effectively hasten the carbonation reaction.

It is challenging to crystalize a thin film of higher melting temperature when deposited on a substrate with comparatively lower melting point. Trading such disparities in thermal properties between a thin film and its substrate can significantly impede material processing. We report a novel solid-state crystallization process for annealing of high melting point molybdenum thin films. A systematic investigation of laser induced annealing from single pulse to high pulse overlapping is reported upon scanning at fluences lower than the threshold required for the damage/ablation of molybdenum thin films. The approach allows better control of the grain size by changing the applied laser fluence. Atomic force microscopy surface morphology and x-ray diffraction (XRD) analysis reveal significant improvements in the average polycrystalline grain size after laser annealing; the sheet resistance was reduced by 19% of the initial value measured by a Four-point probe system. XRD confirms the enlargement of the single crystal grain size. No melting was evident, although a change in the close packing, shape and size of nanoscale polycrystalline grains is observed. Ultrashort laser induced crystallinity greatly enhances the electrical properties; Hall measurements reinforced that the overall carrier concentration increases after scanning at different laser fluences. The proposed method, based on the aggregation and subsequent growth of polycrystalline and single crystal-grains, leading to enhanced crystallization, has potential to be applicable in thin film processing industry for their wide applications.

We demonstrate that a passive non-contact diagnostic technique, radio emission spectroscopy (RES), provides a sensitive monitor of currents in a low pressure radio frequency (RF) plasma. A near field magnetic loop antenna was used to capture RF emissions from the plasma without perturbing it. The analysis was implemented for a capacitively coupled RF plasma with an RF supply at a frequency of 13.56 MHz. Real-time measurements are captured in scenarios relevant to contemporary challenges faced during semiconductor fabrication (e.g. window coating and wall disturbance). Exploration of the technique for key equipment parameters including applied RF power, chamber pressure, RF bias frequencies and chamber wall cleanliness shows sensitive and repeatable function. In particular, the induced RES signal was found to vary sensitively to pressure changes and we were able to detect pressure and power variations as low as ~2.5 %/mtorr and ~3.5 %/watt, respectively, during the plasma processing during a trial generic plasma process. Finally, we explored the ability of RES to monitor the operation of a multiple frequency low-pressure RF plasma system (f1 = 2 MHz, f2 = 162 MHz) and intermixing products which suggests strongly that the plasma sheaths are the primary source of this non-linear diode mixing effect.

We propose a novel low temperature annealing method for selective crystallization of gold thin films. Our method is based on a non-melt process using highly overlapped ultrashort laser pulses at a fluence below the damage threshold. Three different wavelengths of a femtosecond laser with the fundamental (1030 nm), second (515 nm) and third (343 nm) harmonic are used to crystallize 18-nm and 39-nm thick room temperature deposited gold thin films on a quartz substrate. Comparison of laser wavelengths confirms that improvements in electrical conductivity up to 40% are achievable for 18-nm gold film when treated with the 515-nm laser, and the 343-nm laser was found to be more effective in crystallizing 39-nm gold films with 29% improvement in the crystallinity. A two-temperature model provides an insight into ultrashort laser interactions with gold thin films and predicts that applied fluence was insufficient to cause melting of gold films. The simulation results suggest that non-equilibrium energy transfer between electrons and lattice leads to a solid-state and melt-free crystallization process. The proposed low fluence femtosecond laser processing method offers a possible solution for a melt-free thin film crystallization for wide industrial applications.