Browsing by study line "Oorganisk materialkemi"

Photocatalysis is a versatile method to use solar energy for chemical processes. Photocatalytic materials absorb light to generate energetic electron-hole pairs that can be used for redox reactions in production of hydrogen and other chemicals, degradation of pollutants, and many other applications. BiVO4 is a visible light absorbing oxide semiconductor with a band gap of about 2.4 eV, and it has received a lot of attention as a standalone photocatalyst and as a photoanode material. The literature part of this thesis explores how the electronic structure of semiconductors and the different processes in photocatalysis together affect the efficiency of the method. Semiconductor materials are classified based on their chemical composition and compared by selecting most researched materials as examples. Various strategies to improve the photocatalyst material properties are also discussed. Many strategies, such as nanostructured photocatalysts, benefit from deposition of semiconductor thin films. Atomic layer deposition (ALD), as a highly conformal and controllable chemical vapor deposition method, is an excellent choice for depositing semiconductors and various interfacial layers. The literature review also includes a survey of ALD processes for Bi2O3 and V2O5 and a thorough analysis of the existing BiVO4 ALD processes. From the selection of binary ALD processes, bismuth(III) 2,3-dimethyl-2-butoxide (Bi(dmb)3), tetrakis(ethylmethylamido)-vanadium(IV) (TEMAV), and water were chosen as precursors to develop a new ALD process for BiVO4. The binary processes were combined in various metal precursor ratios both completely mixed in supercycles and as nanolaminates, and the resulting films were annealed to crystallize the BiVO4. X-ray diffraction was used to characterize the crystalline phases of the films, and it was noticed that TEMAV reacts with Bi2O3 to make metallic bismuth, but it is reoxidized by annealing. Composition of the films was investigated with energy dispersive X-ray spectrometry and time-of-flight elastic recoil detection analysis (ToF-ERDA). Some sensitivity to process conditions was observed in the deposition, as the metal stoichiometry varied in unexpected manner between some sets of experiments. ToF-ERDA depth profiles also revealed that mixing of the nanolaminate layers was incomplete with annealing temperatures below 450 °C and with laminate layers over 10 nm in thickness. Scanning electron microscopy was used to study the morphology of the films and revealed a granular, non-continuous structure. The optical properties of the films grown on soda-lime glass were investigated with UV-vis spectrophotometry. The band gaps of the films were estimated to be 2.4–2.5 eV. The nanolaminate approach to depositing the films was deemed the best, as it avoids most of the reduction of bismuth by TEMAV. However, it is still not clear why this process is so sensitive to process conditions. This should be investigated to further optimize the film stoichiometry. The morphology of the films might be improved by using different substrates, but it is not a critical aspect of the process as there are methods to passivate the exposed substrate surface. Overall, this process has potential to deposit excellent BiVO4 films that are suitable for further research pertaining their photocatalytic properties and modifications such as nanostructured or doped photoanodes.

Plasmonic catalysis utilises light energy to drive chemical reactions. Compared to conventional catalytic processes, which are run by high temperatures and pressures, light-driven processes can lower energy consumption and increase selectivity. Conventional plasmonic nanoparticles (Ag, Au) are relatively scarce and expensive, and therefore the use of materials with earth-abundant elements in plasmonic catalysis is widely pursued. Despite their good optical properties, plasmonic nanoparticles are often unsuitable catalysts. Hybrid catalysts, structures consisting of a light-harvesting plasmonic part and a catalytical centre of different material, have emerged as an opportunity to address these challenges and obtain desired properties. This thesis consists of two parts: In the first part, properties of plasmonic materials are described, and previous studies of hybrid catalysts with earth-abundant plasmonic materials are reviewed. Experimental work on plasmonic-catalytic nanohybrids, with TiN as the plasmonic part and Pd as the catalytic entity, is described in the second part. In this context, a Pd/TiN (Pd nanoparticles supported into TiN) catalyst was synthesised, characterised and applied to test catalytical reactions. Contrary to the hypothesis, light-induced rate enhancement was not observed in our current catalytical studies. These results call for further optimisation of synthesis and reaction conditions to prepare an earth-abundant, light-active catalyst.

Ensuring adequate air quality is integral to healthy living. Since in modern societies the majority of time is spent indoors, understanding indoor air pollution and the means of air purification are of great importance. Adverse health effects are induced by volatile organic compounds (VOC) that originate from everyday activities and our surroundings. Photocatalysis is a radiation-activated chemical transformation that can be used to decompose organic pollutants into harmless constituents. However, existing air purification solutions employing photocatalysis often rely on UV light limiting the use of solar radiation. Titanium dioxide is a popular photocatalyst material, but it requires modification to its electronic properties to respond to visible light. An established approach is to introduce atoms of other dopant elements into the titania lattice. Atomic layer deposition (ALD) is a thin film deposition technique widely studied especially in metal and metal oxide research. Following from the principle of sequential saturation of the surface, control over the size and composition of the film may reach atomic level. Since the chemical configuration of a doped TiO2 film is of utmost importance to successful modification, ALD is an excellent tool to examine suitable photocatalytic TiO2 chemistries. Furthermore, thin solid films of catalytically active material would have a distinguished advantage for deployment in real-life settings over their powderous counterparts. The literature review of this thesis explores the semiconductor photocatalysis with an eye on its suitability to indoor air purification. The motivation is to give the reader a view on the air quality issue, the existing technological solutions and how a thin film photocatalyst could supplement the field. Titanium dioxide doping concepts are introduced to elucidate the rationale behind the experimental efforts. The experimental part describes a development project to deposit visible-light responding photocatalysts. Titanium dioxide thin films co-doped with nitrogen and zinc/fluorine were grown on steel plates. An in-house built reactor system was used to study acetaldehyde degradation under irradiation. Unfortunately, the reactor experienced a malfunction, rendering a large part of the results futile. Moreover, months of valuable time were lost in chasing a mirage of fallacious data. In the end an ALD grown photocatalyst responding to visible light could not be materialized.

Bimetallic core-shell catalysts represent a new pathway to create highly selective and highly active catalysts. This can be done by using a relatively inactive metal as the core material and a more active metal as the shell material. The composition of both the core and shell structure can then be altered in order to tune the selectivity of the nanocatalyst. The synergistic effects of using bimetallic core-shell catalysts arise in part from the misfit strain that is encountered as a result of the difference in lattice spacings between the core and shell materials. The catalysts investigated here consist of an Au core and a Pd shell. Particles with four different Pd shell thicknesses were synthesized and the corresponding strain was measured. There is a 5.07% difference in the lattice spacings between Au and Pd, we therefore expect strain values to be near this amount. In this work, we directly measured the displacement fields that arise due to lattice mismatch in Au-Pd nanorods using High Resolution Scanning Transmission Electron Microscopy (HRSTEM) and 4D Scanning Transmission Electron Microscopy (4D-STEM). The strain was then calculated using three different analytical methods: Geometric Phase Analysis (GPA), Gaussian Peak Fitting, and nanodiffraction. These methods all measure the variations in local lattice parameters and plot these values for every pixel in the original STEM image, this results in a 2D strain map. These maps were then compared to see which produced the highest quality strain quantification.

Aluminium nitride is a piezoelectric material commonly used in piezoelectric microelectromechanical systems (MEMS) in the form of thin films deposited by sputtering. AlN-based devices are found in wireless electronics in the form of acoustic filters, but they also have prospective applications in a wide variety of sensor systems. To enhance the piezoelectric properties of AlN, some of the Al can be replaced with scandium, which is required for next-generation devices. However, addition of Sc makes both the deposition and patterning of the film more difficult. This work focuses on patterning of AlN and Sc0.2Al0.8N thin films with wet etching. Both materials are etched anisotropically, which in theory enables etching the materials with little deviation from the mask dimensions. However, in practise, undercutting at the mask edges occurs easily making the structures narrower compared to the etch mask. This work investigates and compares the mechanisms and etch rates of AlN and Sc0.2Al0.8N. Tetramethyl ammonium hydroxide was mostly used for etching, but also H3PO4 and H2SO4 were tested. Addition of 20 atom-% Sc lowered the etch rate of the material and resulted in more undercutting. The causes behind mask undercutting were examined by using 11 differently deposited etch masks, and the undercutting was minimized by optimizing the mask deposition, using thermal annealing, and optimizing the etching temperature. Finally, the work identifies and discusses the relevant factors in depositing and patterning the AlN, ScxAl1-xN and mask films.