Atomic layer deposition (ALD) is a technique by which surface-based reactions between a precursor molecule (often metal-containing) and a co-reactant (e.g. H2O, O2 or H2) yield highly uniform and conformal (ultra-)thin films. The precursor and co-reactant are each delivered in the gas phase, separated from one another by inert gas purge steps. The self-limiting nature of these surface-based reactions allows the thickness of the film to be controlled solely by the number of ‘precursor – purge – co-reactant – purge’ cycles. This nano-scale control of film thickness allows for a large number of applications such as in flat panel displays, fuel and solar cells, and microelectronic devices. The first goal of this project was the pursuit of new low-temperature methods for main group elemental ALD using silyl-substituted precursor molecules. The second goal of the project was the development of alternative methods for thin film deposition of group 4 (M = Hf, Zr) oxides that would encourage effective (ie. void-free) filling of narrow (<20 nm) trenches in high-aspect-ratio (HAR) substrates. This thesis includes the development of new precursor molecules and reaction pathways, evaluation of precursor molecular structures, thermal stability, volatility and solution reactivity, identification of appropriate experimental conditions for ALD, and characterization of the resulting thin films. ALD of elemental antimony was achieved on hydrogen-terminated silicon (H-Si) and SiO2/Si substrates using Sb(SiMe3)3 (2-1) and SbCl3 in the temperature range 23- 65 °C. The mirror-like films were confirmed to be composed of crystalline antimony by XPS (for the film deposited at 35 °C) and XRD, with low impurity levels and strong preferential orientation of crystal growth relative to the substrate surface. To the best ofour knowledge, this is the first example of room temperature thermal ALD (with demonstrated self-limiting growth) of a pure element. Film growth at 35 °C exhibited a substrate-enhanced mechanism, characterized by faster film growth for the first ~125 ALD cycles, where substantial deposition is occurring on the original substrate surface (GPC (growth-per-cycle) = 1.3 Å on SiO2/Si, and 1.0 Å on H-Si), and slower film growth (GPC = 0.40 Å on SiO2/Si, and 0.27 Å on H-Si) after ~125 cycles, once much of the initial substrate surface has been covered. Films deposited using 500-2000 ALD cycles were shown to be continuous by SEM. The use of less than 250 cycles afforded discontinuous films. However, in this initial growth phase, when deposition is occurring primarily on the original substrate surface, in-situ surface pre-treatment by Sb(SiMe3)3 or SbCl3 (50 x 0.4 or 0.8 s pulses), followed by the use of longer precursor pulses (0.4 or 0.8 s) during the first 50 ALD cycles resulted in improved nucleation. For example, on H-Si, a continuous 6.7 nm thick film was produced after initial pre-treatment with 50 x 0.8 s pulses of SbCl3, followed by 50 ALD cycles using 0.8 s pulses. The use of longer ALD pulses in the first 50 ALD cycles following surface pre-treatment is likely required in order to achieve complete reactivity with an increased density of reactive surface sites. Boranes featuring bulky silyl or sterically unencumbered trimethylgermyl groups, in combination with a stabilizing dimethylamido group, were pursued as potential precursors for ALD of elemental boron. This ALD process would employ a boron trihalide (BX3; X = F, Cl, Br, I) co-reactant, exploiting the thermodynamically favourable formation of tetrel-halide bonds as a driving force. This work required multistep syntheses of alkali metal silyl reagents, {(Me3Si)3Si}Li(THF)2 (3-1) and tBu3SiNa(THF)n (3-2), and previously un-isolated [Me3GeLi(THF)2]2 (3-3), and their reactions with B(NMe2)Cl2 (3-4). The boranes {(Me3Si)3Si}2B(NMe2) (3-8) and (tBu3Si)(Me3Ge)B(NMe2) (3-12) were successfully synthesized, spectroscopically and crystallographically characterized, and assessed for their suitability as precursor molecules for boron ALD. Unfortunately, deposition attempts on SiO2/Si using 3-8 and BCl3 led to minor film growth (GPC = 0.01 Å). However, the enhanced volatility and solution-state reactivity of 3-12 in comparison to 3-8 makes it a promising precursor candidate for future ALD reactor studies. Attempts to synthesize bis(trimethylgermyl)(dimethylamido)borane from the 2:1 reaction of 3-3 with 3-4 resulted in the formation of a lithium trigermylamidoborate, {(Me3Ge)3B(NMe2)}Li(THF)2 (3-13). ALD can give rise to uniquely uniform and conformal ultra-thin films, but voids often remain after attempted filling of narrow high-aspect-ratio trenches. To achieve void-free trench-filling, ALD (or CVD; chemical vapour deposition) methods which deposit a flowable material are desirable, and this initially-deposited material can be converted to the target material (e.g. a metal oxide) by post-deposition annealing, or potentially at the deposition temperature on a longer timescale than flowable behaviour. In this work, a new HfO2 ALD process was developed using [Hf(NMeEt)4] in combination with β- hydroxyisovaleric acid (IVA; CMe2(OH)CH2CO2H) that introduces the potential for flowability. Self-limiting growth was observed at 100, 250, and 300 °C, with a GPC of 1.5- 2.2 Å on planar SiO2 substrates. Films deposited at 100 °C consisted of amorphous HfO2 with significant carbon content (~22 at%) and <1 at% nitrogen. After annealing at 400 °C in vacuo for 1 hour, the films were composed of amorphous HfO2 with low (<1 at%) carbon content. The co-reactant in this work, β-hydroxyisovaleric acid, was chosen with the following criteria in mind: Firstly, the carboxylic acid group may be sufficiently acidic to cleave linkages between chemisorbed hafnium species and the surface, generating flowable non-surface-tethered hafnium carboxylate species (with low volatility, so that they are not lost from the surface). Secondly, the hydroxyl groups of the ligands can potentially serve as reactive sites for the hafnium precursor delivered in the next pulse. Thirdly, fairly low-energy pathways should exist for deprotonated IVA ligands to decompose to generate oxide or hydroxide ligands with release of volatile by-products, such as CO2 and isobutene, or acetone and ketene. Experiments to gain insight into the nature of reactivity between [Hf(NMeEt)4] and IVA and a structurally similar carboxylic acid are described. These include (a) solution-state reactions between [Hf(NMeEt)4] and IVA or pivalic acid (tBuCO2H), with formation of [H2NMeEt]2[Hf(κ2-O2CCH2CMe2OH)2(κ2- OC(O)CH2CMe2O)2] (4-1) and [Hf5(μ3-O)4(κ2-O2CtBu)4(μ-O2CtBu)8] (4-2), (b) attempted ALD using pivalic acid (which lacks a hydroxyl group) in place of IVA, and (c) roomtemperature solution reactions between [Hf(NMeEt)4] and 4 equiv. of IVA to form 4-1, followed by removal of volatiles, heating at 200 °C, and volatile/soluble product analysis by NMR spectroscopy and GC-MS headspace analysis. Compounds 4-1 and 4-2 were isolated and crystallographically characterized. Heteroleptic zirconium(IV) complexes were designed, synthesized, spectroscopically and crystallographically characterized, and assessed as potential precursor molecules to enable flowable ZrO2 ALD. The envisaged process would operate via the deposition of oligomeric, one-dimensional chains that, if grown untethered on a functionalized substrate, could potentially flow to the bottoms of trenches. Reaction of one equivalent of H2(acen), H2(cis-Cyacen) or H2(trans-Cyacen) with [Zr(CH2SiMe3)4] at room temperature afforded [Zr(acen)(CH2SiMe3)2] (5-1), [Zr(cis-Cyacen)(CH2SiMe3)2] (5-2) or [Zr(trans-Cyacen)(CH2SiMe3)2] (5-3), respectively (acen = C2H4(NCMeCHC(O)Me)2; Cyacen = 1,2-C6H10(NCMeCHC(O)Me)2). These alkyl compounds are trigonal prismatic in the solid state, and whereas 5-1 and 5-3 decomposed without sublimation above 120 °C (5-10 mTorr), 5-2 sublimed in >95% yield at 85 °C (5-10 mTorr). However, heating solid 5-2 at 88 °C under static argon for 24 hours resulted in extensive decomposition to afford H2(cis-Cyacen) and SiMe4 as the soluble products. Compound 5-2 reacted cleanly with two equivalents of tBuOH to afford [Zr(cis-Cyacen)(OtBu)2] (5-4), but excess tBuOH caused both SiMe4 and H2(cis-Cyacen) elimination. The 1:1 reaction of H2(acen) with [Zr(NMeEt)4] did not proceed cleanly, and 8-coordinate [Zr(acen)2] (5-5) was identified as a by-product; this complex was isolated from the 2:1 reaction. A zirconium amido complex, [Zr(acen)(NMeEt)2] (5-6) was accessed via the reaction of 1 with two equiv. or excess HNMeEt, but decomposed readily in solution at room temperature. More sterically hindered [Zr(acen){N(SiMe3)2}2] (5-7) was synthesized via the reaction of [Zr(acen)Cl2] with two equivalents of Li{N(SiMe3)2}, but was also thermally unstable as a solid and in solution at room temperature. Compounds 5-1 to 5-3, 5-5 and 5-7 were crystallographically characterized. / Dissertation / Doctor of Science (PhD) / The focus of this work is the development of new processes to deposit ultra-thin films of main group elements and transition metal oxides. The deposition method utilized in this work is atomic layer deposition (ALD), which involves the use of a precursor molecule (which contains the target element) and a co-reactant. These chemical species must be appropriately reactive towards one another, and display adequate volatility and thermal stability. The feasibility of a precursor/co-reactant combination can be assessed using solution-state reactivity studies. For main group element ALD, silyl-containing compounds (E(SiR3)3, E = Sb, B) have been investigated as precursors in combination with EX3 (X = F, Cl, Br, I) coreactants, due to the potential for thermodynamically favourable Si-X bond formation to drive the required surface-based reactions. For metal oxide ALD (MO2; M = Hf, Zr), new ALD methods have been proposed to enable gap-free filling of narrow trenches on the surface of a silicon wafer. This work involved the design, synthesis, and evaluation of new ALD precursor molecules and reactions, ALD reactor studies for thin film deposition, and characterization of the resulting films.

Nuclear power plants generate electricity by means of splitting atoms. The basic safety requirements and objectives are to protect the people, society, and the environment from radiological accidents, limit harmful effects of ionizing radiation during operation and take all reasonable practical steps to prevent radiological accidents. Defense in depth is the concept of preventing and mitigate accidents with multiple layers of protection and is applied in nuclear power plants. Safety systems and safety criteria from regulatory authorities are put in place to ensure defense in depth and fulfill the safety requirements and objectives. The high-pressure injection system injects high concentrations of boron acid into the primary side of the plant, reducing reactivity and power. It has three lines connected to the cold leg of three out of four main coolant loops. Each line uses a piston pump to pump borated water from boron tanks into the primary side. The system is designed to suppress positive reactivity without a pressure drop on the primary side. For this work, the high-pressure injection system is activated at 107% nominal power, a condition for when SCRAM normally is activated. The amount of boron introduced to the system is decided by two main factors, the volumetric flow rate and the boron concentration. System codes for modelling and simulation of power plants have long been used for analysis of reactor dynamic behavior. The modelling and simulation software Apros has been developed for the purpose of modelling nuclear power plant systems. This thesis is conducted at Westinghouse Electric Sweden AB with the purpose of modelling the primary side of a VVER1000. The license, learning material and documentation were provided by the company. A sensitivity study of the boron concentration contra volumetric flow rate of the high-pressure injection system was performed to see if one factor had a larger effect than the other on the primary side. The sensibility study explored two scenarios where reactor trip is unavailable. One scenario where all the control rods are extracted and get stuck and another scenario where all the rods are fully withdrawn, increasing power, temperature and pressure, triggering the pressurizer pressure relief system. The analysis focused on the effects on power and reactor outlet pressure. Results showed that volumetric flow rate affects the system more than boron concentration. In particular, when volumetric flow rate increased to 8.3 m3 /h , the pressure relief system did not activate while it did for 7.3 m3 /h , suggesting that for a limited power increase rate and high enough volumetric flow rate, the high-pressure injection system dampen reactivity, and in extension, pressure enough to not activate the pressure relief system. For future work, the natural continuation of this work is to explore a larger range of boron concentrations and volumetric flow rates. Obtaining validation data and validating the model could yield results that are not purely theoretical. / Kärnkraftverk genererar elektricitet genom att klyva atomer. De grundläggande säkerhetskraven och målen är att skydda människor, samhälle och miljö från radiologiska olyckor, begränsa skadliga effekter av joniserande strålning under drift och vidta alla rimliga praktiska åtgärder för att förhindra radiologiska olyckor. Flernivåskydd (defense in depth) är konceptet för att förebygga och minimera olyckor med flera skyddslager och tillämpas i kärnkraftverk. Säkerhetssystem och säkerhetskriterier från tillsynsmyndigheter har införts för att säkerställa flernivåskydd och uppfylla säkerhetskraven och målen. Högtrycksinsprutningssystemet injicerar höga koncentrationer av borsyra in i kärnkraftverkets primärkrets, vilket minskar reaktivitet och effekt. Den har tre stråk anslutna till den kalla delen av tre av fyra kylkretsar. Varje stråk använder en kolvpump för att pumpa borat vatten från bortankar till primärsidan. Systemet är designat för att dämpa positiv reaktivitet utan tryckfall i primärkretsen. För detta arbete är högtrycksinsprutningssystemet aktiverat vid 107 % nominell effekt, ett villkor för när SCRAM normalt sätt aktiveras. Mängden bor som införs i systemet bestäms av två huvudfaktorer, den volymetriska flödeshastighetenborkoncentrationen. Systemkoder for modellering och simulering av kraftverk har länge används för analys av reaktorns dynamiska beteende. Modellerings- och simuleringsmjukvaran Apros har utvecklats i syfte att modellera kärnkraftverkssystem. Detta examensarbete är utfört på Westinghouse Electric Sweden AB med syftet att modellera primärkretsen av en VVER1000. Licensen, läromedel och dokumentation har tillhandahållits av företaget. En känslighetsstudie av borkoncentrationen och volymetrisk flödeshastighet i högtrycksinsprutningssystemet utfördes för att se om en faktor hade en större effekt än den andra i primärkretsen. Känslighetsstudien undersökte två scenarier där snabb stopp av reaktorn inte var möjlig. Ett scenario där alla styrstavar dras ut och fastnar och ett annat scenario där stavar alla stavar dras ut helt, vilket ökar effekten, temperaturen och trycket vilket utlöser tryckavlastningssytemet. Analysen fokuserade på effekterna på effekt och reaktorns utloppstryck. Resultaten visade att volymetrisk flödeshastighet påverkade systemet mer än borkoncentrationen. I synnerhet, när det volymetriska flödet ökade till 8.3 m3/haktiverades inte tryckavlastningssytemet medan det gjorde det för 7.3 m3/s. Vilket tyder på att för en begränsad effektökning och tillräcklig hög volymetrisk flödeshastighet, reducerar högtrycksinsprutningssystemet reaktiviteten, och i förlängning, trycket tillräckligt för att inte aktivera tryckavlastningssystemet. För framtida arbeten är den naturliga fortsättningen på detta arbete att utforska ett större spann av borkoncentrationer och volymetriska flödeshastigheter. Att erhålla valideringsdata och validera modellen skulle kunna ge resultat som inte var rent teoretiska.

The automotive industry of today faces ever harder requirements from regulatory bodies to increase the fuel efficiency, reduce the carbon footprint and increase the safety of their vehicles. The problem is being tackled in different ways; one of them being the use of innovative materials to reduce the overall weight while improving the crash safety of the vehicle. One such material is 22MnB5, an ultra-high strength (UHS) boron-alloyed steel, capable of reaching tensile strength of 1900 MPa. The weldability is a vital factor for applying boron steel in an efficient way into a vehicle construction. Resistance spot welding (RSW) is, among the different welding methods, the primary joining methods used within the automotive industry. The main challenges with RSW of UHS boron steel is the narrow welding window and increased risk of expulsion compared to conventional automotive steel. The aim of this thesis was evaluating how the weldability of three-sheet UHS boron steel combinations could be improved by applying different innovative welding methods. The methods investigated where; three-pulsed welding, two-pulsed welding with force profile and using hollow-cone electrodes instead of regular electrodes. The different methods where evaluated with welding experiments and analysis of the nugget diameter, vicker hardness comparison and tensile strength test of welding nugget. The results from this thesis shows that the current window of three-sheet combinations with UHS boron steel can be significantly improved by using hollow-cone electrodes in RSW. The results also showed that the width of the current window varied depending on the depth of the hole in the electrode, a deeper hole improved the current window but also increased the oxide build-up. Applying a force profile with lowered electrode force during the welding sequence provided an improved process window compared to the constant electrode force when welding a three-sheet combination containing AlSi-coated boron steel. A three-pulse welding sequence performed better than the reference two-pulse welding schedule but still not good enough to meet VCC acceptance criteria. / Bilindustrin står idag inför allt hårdare krav från tillsynsmyndigheter förbättra bränsleeffektiviteten, minska koldioxidavtrycket och öka säkerheten på deras fordon. Problemet angrips från ett flertal olika vinklar. varav en ökad användning av innovativa material för att minska den totala vikten samtidigt som fordonets kraschsäkerhet bibehålls eller ens förbättras. Ett sådant material är 22MnB5, ett höghållfast (UHS) borstål, kapabelt att uppnå brottgränser på 1900 MPa.  Svetsbarheten är en vital faktor för att kunna applicera borstål på ett effektivt sätt i en fordonskonstruktion. Inom bilindustrin är motståndspunksvetsning (RSW) den dominanta svetsmetoden. De största utmaningarna med att punktsvetsa höghållfast AlSi-belagt borstål är det har ett generellt smalare svetsfönstren, samt den ökade risken för sprut under svetsprocessen, jämfört med konventionella stål. Målet med denna avhandling var att utvärdera hur svetsbarheten av tre-plåtskombinationer med höghållfast AlSi-belagt borstål kunde förbättras genom att applicera innovativa svetsmetoder. De utvärderade metoderna var; tre-pulsad svetsning, två-pulsad svetsning med applicerad kraftprofil, samt användning av ihåliga elektroder istället för vanliga elektroder. Metoderna utvärderades genom svetsexperiment och analys av svetslobens storlek, vicker hårdhets mätning samt brottgränsmätning av svetsloben. Resultaten från denna avhandling visar att svetsbarheten för tre-plåts kombinationer med UHS borstål kan förbättras avsevärt genom att använda ihåliga elektroder för punktsvetsning. Resultaten pekar också på att förbättringen beroende på hålets djup i elektroden. Ett djupare hål gav större förbättringar men ökade också uppbyggnaden av oxid och restmetall i elektroden.  Genom att applicera en kraftprofil, där elektrodkraften sänktes under svetsprocessen kunde svetsbarheten förbättras för två-puls svetsning, jämfört med att ha konstant elektrodkraft, vid svetsning av en tre-plåtskombination innehållande höghållfast AlSi-belagt borstål. En tre-puls svetssekvens utförde bättre än referenspulssvetsschemat men fortfarande inte tillräckligt bra för att uppfylla VCC-acceptkriterierna.

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The efficiency of boron-doped diamond electrodes (BDD) has been investigated by electrolysis of an aqueous solution containing sodium sulfate. A Synthesis StarterKit from Condias was used, which contained the BDD anode with an active surface area of 3.14 cm2, and electrosynthesis was performed in a batch mode reactor. In this report, the electrooxidation of sodium sulfate to sodium persulfate is well reported. The production of persulfate was studied at different cell voltages and electrolyte concentrations. The amount of persulfate produced was determined by the iodometric titration and itwas found that its concentration in the electrolyte was directly proportional to the persulfate concentration, i.e, a larger amount of persulfate could be obtained when the electrolyte was highly concentrated, up to 1 M. For each of the samples the amount of persulfate that theoretically is possible to produce was calculated and subsequently compared to the actual amount of persulfate that was formed, ie. current efficiencies. These current efficiencies were unexpectedly low for all experiments except for one data point. Hydrogen gas was also produced as a by-product at the cathode, but it couldn ot be collected in the present setup. The results and some possible improvements are discussed in the report. / Effektiviteten av att använda bor-dopad diamant (BDD) för elektrosyntes med en vattenlösning innehållande natriumsulfat för att producera persulfat har undersökts. Den utrustningen som använde svar ett Syntes StarterKit från företaget Condias, denna innehöll en cell med BDD som anodmaterial vilken hade en aktiv area på 3,14 cm2. Produktionen av persulfat studerades vid olika cellspänningar och elektrolytkoncentrationer. Mängden av producerad persulfat bestämdes genom titrering. Detv isade sig att koncentrationen av elektrolyten var proportionell mot persulfatkoncentrationen, dvs. mer persulfat producerades vid högre elektrolytkoncentrationer. För varje prov beräknades även det teoretiska antalet mol persulfat som kan åstadkommas och jämfördes sedan med det faktiska antalet mol som producerades, detta gav strömeffektiviteten för den önskade reaktionen. Denna effektivitet var oväntat låg för alla prov förutom ett i experiment 4. Vätgas producerades som en biprodukt vid katoden, men på grund av begränsad tillgång till utrustning och tid kunde denna gas inte samlas uppför vidare analys. Resultaten och möjliga förbättringar diskuteras även i rapporten.

Many attempts have been made to prepare aryl boronic acids and their esters which show a preferential affinity for tumor tissues for use in radiation therapy of neoplatic disorders (1,2). The data of Soloway, as extended and refined by Hansch and his coworkers, successfully correlates the low lipid solubility and electron releasing substituents of phyenl boronic acid derivatives with increased tumor concentration (3,4,5). However, most of these organoboron compounds do not produce a sufficiently high tumor-to-normal tissue boron concentration ratio for practical use in human cancer chemotherapy by the neutron capture technique. The knowledge that several chemical substances are preferentially taken up by tumor tissue provides the medicinal chemist the opportunity of rationally designing potential tumor inhibiting compounds linked to these carrier molecules (6,7). For the initial phase of attempts to successfully combine boronic acids or their esters with tumor concentrating material, it was deemed desirable to prepare a homologous series of aryl mono- and diboronic acids

Pressurized hot water and DTPA-Sorbitol are two relatively new soil boron (B) extraction methods with potential to replace the cumbersome hot water extraction. The objective of this research is to produce data in support of acceptance or rejection of these two alternative B extractions. The three soil tests were used to extract B from samples of calcareous sand and silt loam and limed, loamy fine sand treated with 10 levels of B and incubated for 7 and 28 d. As B application increased so did extractable B with each extraction method. High correlations (r of 0.977 to 0.999) were observed between extractable B and rate of B application with all three methods. Hot water generally extracted the least and pressurized hot water the most B regardless of soil type, rate of application or duration of incubation. Greenhouse and field experiments were conducted on one limed acid and two alkaline soils naturally low in B to test alfalfa response to B fertilizer. Values from the three soil extraction methods were correlated to yield, B tissue concentration and total B removal of alfalfa. In greenhouse studies with varying levels of soil applied B, highly significant relationships exist between extractable soil B and both tissue B concentration and total B removal. Correlations between yield and extractable soil B were impossible to obtain because of a lack of alfalfa yield responses to applied boron. All three methods accurately predict plant B tissue concentrations and total B removal. The field experiment produced a significant positive relationship between total alfalfa yield and extractable B using hot water and pressurized hot water extractions, but not using DTPA-Sorbitol. The results observed in this research support pressurized hot water extraction as the better of the two alternatives to replace hot water extraction in a broad range of soil types.

Yes / Alumina-cubic boron nitride (cBN) composites were prepared using the spark plasma sintering (SPS) technique. Alpha-alumina powders with particle sizes of ∼15 µm and ∼150 nm were used as the matrix while cBN particles with and without nickel coating were used as reinforcement agents. The amount of both coated and uncoated cBN reinforcements for each type of matrix was varied between 10 to 30 wt%. The powder materials were sintered at a temperature of 1400 °C under a constant uniaxial pressure of 50 MPa. We studied the effect of the size of the starting alumina powder particles, as well as the effect of the nickel coating, on the phase transformation from cBN to hBN (hexagonal boron nitride) and on the thermo-mechanical properties of the composites. In contrast to micro-sized alumina, utilization of nano-sized alumina as the starting powder was observed to have played a pivotal role in preventing the cBN-to-hBN transformation. The composites prepared using nano-sized alumina reinforced with nickel-coated 30 wt% cBN showed the highest relative density of 99% along with the highest Vickers hardness (Hv2) value of 29 GPa. Because the compositions made with micro-sized alumina underwent the phase transformation from cBN to hBN, their relative densification as well as hardness values were relatively low (20.9–22.8 GPa). However, the nickel coating on the cBN reinforcement particles hindered the cBN-to-hBN transformation in the micro-sized alumina matrix, resulting in improved hardness values of up to 24.64 GPa.