Bismuth telluride-Bi2Te3 is the most promising material for harvesting thermal energy near room temperature. There are numerous works on Bi2Te3 reporting significantly different transport properties, with no clear connection to the synthetic routes used and the resultant surface chemistry of the synthesized materials. It is of utmost importance to characterize the constituent particles’ surface and interfaces to get a better understanding of their influence on the transport properties, that will significantly improve the material design starting from the synthesis step. Electrophoretic deposition (EPD) is a promising technique, enabling the formation of thick films using colloidally stabilized suspensions of pre-made nanoparticles, which can enable the study of the effect of surface chemistry, in connection to the synthetic route, on the material's transport properties. In order to explore the differences in surface chemistry and the resultant transport properties in relation to the synthetic scheme used, here we report on Bi2Te3 synthesised through two wet-chemical routes in water (Hydro-) and oil (Thermo-) as the solvents. XRD analysis showed a high phase purity of the synthesized materials. SEM analysis revealed hexagonal platelet morphology of the synthesized materials, which were then used to fabricate EPD films. Characterization of the EPD films reveal significant differences between the Hydro- and Thermo-Bi2Te3 samples, leading to about 8 times better electrical conductivity values in the Thermo-Bi2Te3. XPS analysis revealed a higher metal oxides content in the Hydro-Bi2Te3 sample, contributing to the formation of a resistive layer, thus lowering the electrical conductivity. Arrhenius plots of electrical conductivity vs inverse temperature was used for the estimation of the activation energy for conduction, revealing a higher activation energy need for the Hydro-Bi2Te3 film, in agreement with the resistive barrier oxide content. Both the samples exhibited negative Seebeck coefficient (S) in the order of 160–170 mV/K. The small difference in S of Hydro- and Themo-Bi2Te3 films was explained by the effective medium theory, revealing that the magnitude of S is linearly correlated with the surface oxide content. Based on the findings, TE materials synthesized through thermolysis route is recommended for further studies using soft treatment/processing of pre-made TE materials. EPD platform presented here is shown to clearly expose the differences in the electronic transport in connection to nanoparticle surface chemistry, proving a promising methodology for the evaluation of morphology, size and surface chemistry dependence of electronic transport for a wide range of materials.

With the recent advances in thermoelectric (TE) technology, there is an increasing demand to develop thick films that would enable large-scale TE devices. Assembly of TE-films from size and morphology-controlled nano particles has been a challenging issue that can be addressed by the use of electrophoretic deposition (EPD) technique. In this work, morphology-controlled Sb2Te3 nanoparticles were synthesized through microwave assisted thermolysis, which were subsequently used for EPD of TE films on specially developed glass substrates. The electronic transport properties were measured in the temp-range of 22-45 degrees C. The as-made EPD films showed a high initial resistance, ascribed to high porosity and the presence of surface oxide/passivating layers. The impact of two types of small organic molecules-as hexanedithiol and dodecanethiol, on the electronic transport was investigated, resulting in a significant improvement in the electrical conductivity of the films. The XPS analysis suggests that the thiols bind to the surface of nanoparticles through formation of sulfides. Seebeck coefficient in the range of + 160 to + 190 & mu;V/K was measured, revealing the p-type transport through the deposited films. Finally, a power factor of about 2.5 & mu;W/K2.m was estimated the first time for p-type EPD films, revealing the potential of the developed nanoparticles and substrate, the small molecule additives and the EPD process presented in this work.

The world’s increasing demand for energy and supplying this energy dominantlyfrom fossil fuels has a major impact on global climate change. Theenergy crisis has gotten more alarming in the recent years which increasedthe motivation for replacing fossil fuels with greener routes for energy harvest.There are various technologies developed for harvesting energy, andthe ability to recover energy from waste heat at a wide range of temperatures (from room temperature to more than 1000 ^∘C) distinguished thethermoelectric (TE) materials from the rest. The drawback about the thermoelectricdevices is that they are too inefficient to be cost-effective in manyapplications, and the developments in nanotechnology is providing somesolutions to increase the efficiency of these materials and devices.

The field of thermoelectrics suffer from large discrepancy of theresults in the literature, which is generally attributed to the variations inthe materials qualities, urging a need for the development of synthetictechniques that can lead to large-scale TE materials in reasonable timeframe. In this thesis, three different routes for rapid, scalable, and energyefficient, wet-chemical synthetic techniques for bismuth chalcogenidecompounds are presented. Microwave assisted heating during reactionprovided better control over the particle properties while reducing thereaction time and carbon footprint of the synthetic method, leading tomaterials bismuth chalcogenides with promising TE transport propertiesin a scalable and reproducible manner.

Hybrid TE materials, and recently emerging solid-liquid TE materialsconcept, requires fabrication of porous TE films, to study the effect of variousinterfaces, including solid and liquid electrolytes. For this purpose, wedeveloped and optimized the electrophoretic deposition (EPD) process toprepare nanostructured porous TE films by preserving the size and morphologyof the as-synthesized bismuth chalcogenide particles. A new glass based substrate is designed and fabricated to study the electronic transportproperties of the electrically active films prepared via EPD. Using this platform,we could clearly demonstrate the significance of the synthetic methodon the surface chemistry and resultant transport properties of the TE materials.The methods and materials developed in this thesis are expected toimpact and expedite further developments in the field of thermoelectrics.

Världens ökande efterfrågan på energi och att tillhandahålla denna energifrämst från fossila bränslen har en betydande inverkan på den globalaklimatförändringen. Energikrisen har blivit allt mer alarmerande de senasteåren, vilket har ökat motivationen att ersätta fossila bränslen med grönaenergilösningar. Det har utvecklats olika tekniker för energiutvinning, menförmågan att återvinna energi från spillvärme vid ett brett temperaturintervall(från rumstemperatur till över 1000 °C) skiljer termoelektriska (TE)material från övriga. Nackdelen med TE-enheter är att de är för ineffektivaför att vara kostnadseffektiva i många tillämpningar, där utvecklingen inomnanoteknik erbjuder vissa lösningar för att öka effektiviteten hos dessamaterial och enheter.

Inom området för TE-material finns det stora avvikelser i resultaten i litteraturen,vilket i allmänhet tillskrivs variationer i materialkvaliteten. Detfinns ett behov av att utveckla syntetiska tekniker som kan leda till högeffektivaTE-material i storskalig produktion på rimlig tid. I denna avhandlingpresenteras tre olika metoder för snabb, skalbar och energieffektiv våtkemisksyntetisering av bismutkalkogenidföreningar. Mikrovågsassisteraduppvärmning under reaktionen gav bättre kontroll över partikelegenskapernasamtidigt som reaktionstiden och koldioxidavtrycket för den syntetiskametoden minskade, vilket resulterade i bismutkalkogenider med lovandeTE-transportegenskaper på ett skalbart och reproducerbart sätt.

Hybrida TE-material och det nyligen framkomna konceptet med fastvätska-TE-material kräver framställning av porösa TE-filmer för att studeraeffekten av olika gränssnitt, inklusive fasta och flytande elektrolyter. Fördetta ändamål har vi utvecklat och optimerat elektroforesdepositionsprocessen(EPD) för att framställa nanostrukturerade porösa TE-filmer genomatt bevara storlek och morfologi hos de syntetiserade bismutkalkogenidpartiklarna. En ett nytt substrat baserat på glas har designats och tillverkats föratt studera de elektroniska transportegenskaperna hos de elektriskt aktivafilmerna som framställts via EPD. Med denna plattform kunde vi tydligt visabetydelsen av syntesmetoden för yt-kemin och de resulterande transportegenskapernahos TE-filmerna. De metoder och material som utvecklats idenna avhandling förväntas påverka och påskynda vidareutvecklingen inomforskningsområdet för TE-material.

Serial femtosecond crystallography (SFX) has become one of the standard techniques at X-ray free-electron lasers (XFELs) to obtain high-resolution structural information from microcrystals of proteins. Nevertheless, reliable sample delivery is still often limiting data collection, as microcrystals can clog both field- and flow-focusing nozzles despite in-line filters. In this study, we developed acoustic 2D focusing of protein microcrystals in capillaries that enables real-time online characterization of crystal size and shape in the sample delivery line after the in-line filter. We used a piezoelectric actuator to create a standing wave perpendicular to the crystal flow, which focused lysozyme microcrystals into a single line inside a silica capillary so that they can be imaged using a high-speed camera. We characterized the acoustic contrast factor, focus size, and the coaxial flow lines and developed a splitting union that enables up-concentration to at least a factor of five. The focus size, flow rates, and geometry may enable an upper limit of up-concentration as high as 200 fold. The novel feedback and concentration control could be implemented for serial crystallography at synchrotrons with minor modifications. It will also aid the development of improved sample delivery systems that will increase SFX data collection rates at XFELs, with potential applications to many proteins that can only be purified and crystallized in small amounts.

Assembly of thermoelectric nanostructures with pre-defined morphology and surface chemistry on solid sub-strates has been one of the challenges for in-plane TE devices. Electrophoretic deposition (EPD) has the potential to be used for this purpose, where the use of non-conductive substrates is required to enable a reliable evaluation of the transport property of electrically active films. Bi2Te3 nanoparticles, which were synthesized using microwave-assisted hydrothermal route, were used for the EPD of thermoelectric films on glass substrates. A special substrate was fabricated using maskless photolithography, to evaluate the electronic transport properties of the TE films without the interference of the substrate. Electrolyte composition was optimized for high mobility of the suspended nanoparticles, and Bi2Te3 EPD films were fabricated with a high deposition rate, reaching 10 mu m/min. Initial EPD films showed high resistivity, ascribed to the surface oxide layer and capping ligands. The resistance was significantly reduced by the addition of a dithiol molecular linker, capable of interconnecting the Bi2Te3 nanoparticles through ligand-exchange. Seebeck coefficient in the range-150 to-180 mu V/K was measured, revealing the transport through the deposited films. Finally, a power factor of 169 nW/K-2.m was estimated, revealing the potential for the application of this technology to large area TE films as active coatings using the developed EPD process.

An epsilon-negative metamaterial (ENM) containing core@shell nanoparticles (NPs) was designed, where silver (Ag) NPs served as core and silica (SiO₂) was used as spacer shell. AgNPs were synthesized in large scale, using microwave-assisted polyol method, in three average particle sizes, as 30, 54, and 61 nm, with a narrow particle size distribution. Optical absorption of Ag NPs was investigated using UV-Vis spectroscopy. Their optical behavior was also theoretically predicted for different thicknesses of the SiO₂ shell immersed in media of different refractive indices using the Clausius Mossotti equation. Based on the results, optimal outputs were obtained with a SiO₂ shell of 10 nm in thickness encompassing 54 nm Ag NPs based on the analytical model and numerical simulations here developed for core-shell structures. Then 10 nm SiO₂ shell was grown on 54 nm Ag NPs by sol-gel synthesis. The NPs were then characterized by UV-Vis, TEM, SEM, EDX, DLS, and zeta potential analyses. The synthesized core-shell NPs can be used to establish epsilon-negative properties in polymer layers within visible range of wavelengths.

Scalable synthetic strategies for high-quality and reproducible thermoelectric (TE) materials is an essential step for advancing the TE technology. We present here very rapid and effective methods for the synthesis of nanostructured bismuth telluride materials with promising TE performance. The methodology is based on an effective volume heating using microwaves, leading to highly crystalline nanostructured powders, in a reaction duration of two minutes. As the solvents, we demonstrate that water with a high dielectric constant is as good a solvent as ethylene glycol (EG) for the synthetic process, providing a greener reaction media. Crystal structure, crystallinity, morphology, microstructure and surface chemistry of these materials were evaluated using XRD, SEM/TEM, XPS and zeta potential characterization techniques. Nanostructured particles with hexagonal platelet morphology were observed in both systems. Surfaces show various degrees of oxidation, and signatures of the precursors used. Thermoelectric transport properties were evaluated using electrical conductivity, Seebeck coefficient and thermal conductivity measurements to estimate the TE figure-of-merit, ZT. Low thermal conductivity values were obtained, mainly due to the increased density of boundaries via materials nanostructuring. The estimated ZT values of 0.8-0.9 was reached in the 300-375 K temperature range for the hydrothermally synthesized sample, while 0.9-1 was reached in the 425-525 K temperature range for the polyol (EG) sample. Considering the energy and time efficiency of the synthetic processes developed in this work, these are rather promising ZT values paving the way for a wider impact of these strategic materials with a minimum environmental impact.

The solution synthesis route as a scalable bottom-up synthetic method possesses significant advantages for synthesizing nanostructured bulk thermoelectric (TE) materials with improved performance. Tuning the composition of the materials directly in the solution, without needing any further processing, is important for adjusting the dominant carrier type. Here, we report a very rapid (2 min) and high yield (>8 g/batch) synthetic method using microwave-assisted heating, for the controlled growth of Bi2-xSbxTe3 (x: 0-2) nanoplatelets. Resultant materials exhibit a high crystallinity and phase purity, as characterized by XRD, and platelet morphology, as revealed by SEM. Surface chemistry of as-made materials showed a mixture of metallic and oxide phases, as evidenced by XPS. Zeta-potential analysis exhibited a systematic change of isoelectric point as a function of the material composition. As-made materials were directly sintered into pellets by using spark plasma sintering process. TE performance of Bi2-xSbxTe3 pellets were studied, where the highest ZT values of 1.04 (at 440 K) for Bi2Te3 and 1.37 (at 523 K) for Sb2Te3 were obtained, as n- and p-type TE materials. The presented microwave-assisted synthesis method is energy effective, a truly scalable and reproducible method, paving the way for large scale production and implementation of towards large-area TE applications.

Bismuth telluride-Bi2Te3 is a promising material for harvesting thermal energyfor applications near room temperature, where large-area applications requirenew methods of depositing pre-made particulate materials. Electrophoretic deposition(EPD) technique has the promise of enabling the formation of thickfilms using colloidally stabilized suspensions of pre-made nanoparticles. It isvery important to understand the thermoelectric (TE) materials’ performancein relation to the synthetic process, to enable promising and scalable materialstechnologies. EPD films allow to study the effect of surface chemistry, stronglylinked to the synthetic route, on the material’s physico-chemical and transportproperties. Here we report on the synthesis of Bi2Te3 through wet-chemicalreactions performed in two different media as water (hydrothermal-Hydro) andoil (thermolysis-Thermo). Synthesized materials possess platelet morphology,which were then used to fabricated EPD films on specially developed glass substrates. Characterization of the materials and films reveal significant differencesbetween the surface chemistry of the EPD films of Hydro- and Thermo-Bi2Te3samples, where a higher content of metal oxide phases are observed in the Hydro-Bi2Te3 sample. This has a big impact the electronic transport properties, asrevealed by about nine times higher resistance, confirmed by significantly higheractivation energy, of the Hydro-Bi2Te3 film as compared to the Thermo-Bi2Te3film. Slight difference in the Seebeck coefficient (S) was explained by the effectivemedium theory, revealing that the magnitude of S is linearly correlatedwith the surface oxide content. Based on the findings, TE materials synthesizedthrough thermolysis route is recommended for future studies focusing on EPD of TE materials.