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One of the most common methods to analyse silicon materials is Raman-spectroscopy.[1] More recently there is a focus in the analysis of lattice deformations during sample preparations.[2] These deformations not only increase the chance of crack formation but also increases the chemical reactivity of the silicon towards etch processes or oxidation processes.[3] In this contribution, we will present our latest results on the influence of lattice deformations induced by scratches and saw damage on the etch rate of potassium hydroxide. The lattice deformation will be measured using Raman-microscopy and correlated with the height difference measured with confocal microscopy. It will be shown that the etch rate strongly depends on the lattice deformation and that the etch rate will increase by up to the factor 10 in areas with tensile deformation.
The present study is focused on the question of how lattice strain mechanically introduced into silicon alters the chemical reactivity of the silicon atoms that are affected by the strain field on a microscopic length scale. The magnitude and local distribution of lattice strain are extracted from confocal Raman microscopy measurements. The reactivity of Si is expressed by the etch rate of Si after treatment with HF–HNO3–H2SiF6 mixtures. Then, the local etch rate is calculated from the local etch depth as determined by confocal microscopy. It has been found that tensile strain leads to the highest enhancement of the etch rate, followed by a compressive strain increase in the etch rate.
The stoichiometry and kinetics of wet chemical etching of silicon in HF/HNO3 and HF/HNO3/H2SiF6 mixtures was investigated. The side reactions and main reaction pathways were identified by quantifying all reaction products. The relationship between the concentration of undissociated HNO3 and the consumption of HNO3, as well as the formation of H2 as a function of the mixing ratios were found by varying the etching mixture composition systematically.
Based on the etching rates determined, kinetic models for the reaction- and diffusion-controlled reaction mechanism are presented as well as the interrelation between the etchant composition and the transition between reaction- and diffusion-controlled etching.
Measurement of the temperature dependence of lattice deformations in silicon using Raman microscopy
(2019)
The effect of heating and cooling in the range of 25–900 °C on the lattice deformations of diamond wire-sawn polycrystalline and scratched monocrystalline silicon surfaces was studied in detail using Raman microscopy. Mechanically treated silicon surfaces contain tensile or compressive strained silicon with varying deformation strength and areas with high-pressure silicon phases and amorphous silicon. It is shown that compressive deformed silicon relaxes after heating the sample to 600 °C, while tensile deformed silicon only relaxes after multiple heating and cooling cycles. Raman measurements during the heating and after the cooling phases reveal the individual thermal expansion and relaxation behavior of the deformed silicon states. Compressive deformed silicon relaxes during the heating phase, while tensile deformed silicon relaxes during the cooling phase. It is, therefore, possible to separately relax certain deformation states using thermal annealing without changing the topography of the surface.
Measurement of the temperature dependence of lattice deformations in silicon using Raman microscopy
(2018)
One of the most common methods to analyse silicon materials is Raman-spectroscopy.[1] More recently there is a focus in the analysis of lattice deformations during sample preparations.[2] These deformations not only increase the chance of crack formation but also increases the chemical reactivity of the silicon towards etch processes or oxidation processes.[3] In this contribution, we will present our latest Raman evaluation technique for silicon lattice deformation and a way to control them using rapid thermal annealing. The transitions and relaxation of different lattice deformation states after the rapid heating to up to 900°C will be analysed in detail, while also the recrystallisation of amorphous silicon will be discussed from the aspects of lattice deformations. It will be shown that during the tempering the lattice deformation on scratched, indented or diamond wire sawn samples homogenises to a mainly weak tensile deformed state and that these homogenisation processes happen only up to certain critical temperatures.
The nuclear magnetic resonance (NMR) method was applied for tracking boron impurities in the refining process of metallurgical grade (MG) silicon. From the NMR signal of the 11B isotope at an operating temperature 4.2 K, the boron concentration can be estimated down to the order of 110 wppm B. After melting and resolidification of MG-Si alloyed with Ca and Ti, a major fraction of B impurities remains in the Si solid solution as inferred from the characteristic NMR frequency. The alloying element Ti does not form substantial fractions of TiB2. Acid leaching of crushed powders of MG-Si alloyed with Ca and Ti can diminish the initial impurity content of B suggesting its accumulation in the grain boundary phases.
The effect of strain through mechanical processing on the formation of silicon dioxide, one of the most important chemical reactions for the fabrication of semiconductors, biosensors or photovoltaics, has not yet been studied in detail. In this study, we use the surface modification of silicon by alkylsilanes and Raman microscopy techniques to visualise where different oxidants react preferentially on mechanically processed surfaces. We found that HNO3, H2O2 as well as H2SiF6 only oxidise tensile strained silicon areas and do not oxidise unstrained silicon even after long reaction times. Furthermore, a comparison between H2O2 and HNO3 in the presence of HF was also carried out and it was shown that H2O2/HF only etches away tensile strained areas, whereas HNO3/HF initially attacks the tensile strained areas but also forms NOx species. These NOx species then lead to a strain unselective, geometry-based etching mechanism. These results lead to new possibilities in strain lithography,high-precision etching, as well as in the structuring of biosensors and localisation of surface modifications.
The texturization process during horizontal acidic etching of multi-crystalline silicon wafers
(2014)
Horizontal wet-chemical etching of silicon wafers in an HF/HNO3/H2SiF6 mixture is the most widely-used technique to texturize multi-crystalline silicon wafers for solar cell production. For the first time, the etch rates were determined separately for the upper and lower side during the horizontal texturization and the their different morphologies. The dependency of the surface morphology from the etch rate and etch depth is proven. Furthermore, the influence of the temperature and stirring rates on the morphological development for the upper and lower side of the wafer were examined. From temperature-dependent measurements, activation energies in the range from 17 kJ/mol to 40 kJ/mol on the upper side and from 23 kJ/mol to 40 kJ/mol on the lower side dependent from the etching time were determined. The observed results reveal a connection between the etch depth, the agitation of the etch solution, the morphology and the reflectivity of the separate wafer sides.
The stoichiometry of wet chemical etching of silicon in concentrated HF/HNO₃ mixtures was investigated. The formation of nitrogen species enriched in the etching mixture and their reactivity during the etching process was studied. The main focus of the investigations was the comprehensive quantification of the gaseous reaction products using mass spectrometry. Whereas previously it could only be speculated that nitrogen was a product, its formation was detected for the first time. The formation of hydrogen, N₂, N₂O and NH₄⁺ showed a dependence on the etching bath volume used, which indicates the formation of nitrogen compounds by side reactions. Simultaneously, the ratio of the nitrogen oxides, NO and NO₂, formed decreases with increasing etching bath volume, while nitric acid consumption increases, so that the formation of NO₂ could also be identified as a side reaction. Based on the stoichiometries obtained, a new reaction scheme for the reduction of nitric acid during etching in HF/HNO₃ mixtures and an electron balance for the oxidation of silicon is presented.
In an effort to develop a cost-efficient technology for wireless high-temperature surface acoustic wave sensors, this study presents an evaluation of a combined method that integrates physical vapor deposition with electroless deposition for the fabrication of platinum-based planar antennas. The proposed manufacturing process becomes attractive for narrow, thick, and sparse metallizations for antennas in the MHz to GHz frequency range. In detail, narrow platinum-based lines of a width down to 40 μm were electroless-deposited on γ-Al2O3 substrates using different seed layers. At first, the electrolyte chemistry was optimized to obtain the highest deposition rate. Films with various thickness were prepared and the electrical resistivity, microstructure, and chemical composition in the as-prepared state and after annealing at temperatures up to 1100 ∘C were evaluated. Using these material parameters, the antenna was simulated with an electromagnetic full-wave simulation tool and then fabricated. The electrical parameters, including the S-parameters of the antenna, were measured. The agreement between the simulated and the realized antenna is then discussed.
The molecular absorption of the diatomic AlF molecule in the C2H2/N2O flame was studied using a highresolution continuum source flame atomic absorption spectrometer. AlF has a structured absorption spectrum in the range of 227.30 nm and 227.80 nm. From this band system, the remarkably narrow absorption band at 227.66 nm proved to be the optimum for analytical purposes. The signal intensity was studied as a function of the C2H2 : N2O ratio, the aspiration flow, and the aluminum concentration added to the analytical solution to generate the AlF molecules in the flame. The AlF molecule formation is significantly affected by the bonding state of the fluorine source used. Compared to ionic bound fluorine, organic bound fluorine leads to a markedly less sensitive molecular absorbance of AlF. Furthermore, several ions, such as Na+, K+ and NH4+, and acids, such as HCl, CH3COOH, and HNO3, affect the AlF signal intensity severely. It has to be concluded that the determination of fluorine by AlF F MAS only leads to reliable analytical results in simple matrices.
The present work describes a completely new approach to the solidification refinement of metallurgical-grade silicon. The new process comprises the following steps: (i) The first step involves adding auxiliary metals to the molten silicon in order to segregate the metallic and non-metallic impurities in the secondary phase after cooling. (ii) The melt is rapidly cooled in the cellular solidification regime. This generates a Si microstructure with a defined cell size in which all cell boundaries are surrounded by the secondary phase. Furthermore, the secondary phase should form an interconnected three-dimensional network. (iii) The solids are crushed by shockwaves using electrohydraulic fragmentation techniques. The shockwaves lead to preferential crushing at the interface between the silicon and the secondary phase. (iv) The secondary phases are fast and effectively removed by microwave-assisted high-pressure leaching that was newly developed for this process. The potential of the new refinement procedure is demonstrated with auxiliary metals Ca, Al, and Ti. This new procedure yields a significant decrease in phosphorous and metal impurities.
The silica solubility of aggregates is one of the most important components of the alkali-silica reaction.
It is a surface-controlled process that always still requires more detailed studies to better understand the reaction mechanism.
Since strained quartz releases more SiO2 into the pore solution, the properties of grains, crystals and their structure can should be directly quantified. In other work, various possibilities were tested for this purpose in order to obtain analyses of the surface and to correlate these with the mortar bar tests, for example. However, a quantifiable direct measurement of quartz crystal states with satisfactory results has not yet been performed.
In this thesis polarization and reflected light microscopy in combination with Raman and confocal microscopy is used to obtain quantifiable data by direct measurement of the strained crystals.
First measurements show new surprising signals besides the Raman main peak of the quartz. Such signals cannot be found on the whole sample, but only at places where strains are expected, e.g. at contact zones between different quartz crystals or cracks and sometimes inside of quartz grains too.
Thus, a method may have been found to quantify the strained state of different quartz crystals in natural quartzite rocks.