Academic literature on the topic 'Deep eutectic solvent-based systems'

Fabrication of current generation integrated circuits involves the creation of multilevel copper/low-k dielectric structures during the back end of line processing. This is done by plasma etching of low-k dielectric layers to form vias and trenches, and this process typically leaves behind polymer-like post etch residues (PER) containing copper oxides, copper fluorides and fluoro carbons, on underlying copper and sidewalls of low-k dielectrics. Effective removal of PER is crucial for achieving good adhesion and low contact resistance in the interconnect structure, and this is accomplished using wet cleaning and rinsing steps. Currently, the removal of PER is carried out using semi-aqueous fluoride based formulations. To reduce the environmental burden and meet the semiconductor industry's environmental health and safety requirements, there is a desire to completely eliminate solvents in the cleaning formulations and explore the use of organic solvent-free formulations.The main objective of this work is to investigate the selective removal of PER over copper and low-k (Coral and Black Diamond®) dielectrics using all-aqueous dilute HF (DHF) solutions and choline chloride (CC) - urea (U) based deep eutectic solvent (DES) system. Initial investigations were performed on plasma oxidized copper films. Copper oxide and copper fluoride based PER films representative of etch products were prepared by ashing g-line and deep UV photoresist films coated on copper in CF4/O2 plasma. PER removal process was characterized using scanning electron microscopy and X-ray photoelectron spectroscopy and verified using electrochemical impedance spectroscopy measurements.A PER removal rate of ~60 Å/min was obtained using a 0.2 vol% HF (pH 2.8). Deaeration of DHF solutions improved the selectivity of PER over Cu mainly due to reduced Cu removal rate. A PER/Cu selectivity of ~20:1 was observed in a 0.05 vol% deaerated HF (pH 3). DES systems containing 2:1 U/CC removed PER at a rate of ~10 and ~20 Å/min at 40 and 70oC respectively. A mixture of 10-90 vol% de-ionized water (W) with 2:1 U/CC in the temperature range of 20 to 40oC also effectively removed PER. Importantly, etch rate of copper and low-k dielectric in DES formulations were lower than that in conventional DHF cleaning solutions.

Electronically conducting polymers based on functionalised thiophenes and pyrroles have continued to stimulate academic interest as well as starting to be employed in practical applications and uses. This thesis describes studies of the electronic properties of mixed thiophene-pyrrole polymers (based on custom synthesised mixed monomer precursors) and polymers electrodeposited from commercially available monomers, pyrrole and 3,4-ethylenedioxythiophene, in respect to energy storage applications including batteries and ion selective membranes. In such applications the movement of ion and solvent through the polymer film during oxidation and reduction cycles is critical to application and function, e.g. charging rate, metal ion permeability or adhesion stability. Recently the unexpected behaviour of polypyrrole in choline chloride based ionic liquids has been described. These liquids are especially attractive because of their unique solubility profiles, high stability, low volatility and low toxicity. This thesis describes the electrochemical characterisation, DC capacitance behaviour and ion/solvent transport properties of conducting polymers using a range of electrochemical methodologies in combination with acoustic impedance electrochemical quartz crystal microbalance techniques (EQCM) and X-Ray Photo-electron Spectroscopy (XPS). The behaviour of several mixed thiophene-pyrrole films, polypyrrole and poly 3,4-ethylenedioxythiophene in different electrolyte media; deep eutectic solvents (DESs), conventional organic solvents and aqueous media are contrasted in this thesis. PEDOT and one of the mixed thiophene-pyrrole polymers (poly 2-(thiophene-2-yl)-1H pyrrole) gave the highest DC capacitances of the polymers investigated, with high values observed in both choline chloride based (Type III) and zinc based (Type IV) DESs. The ion dynamics of the polymers p-doping in the DESs, observed to fit gravimetric data recorded, was able to show a marked difference in the ion transfers between DES types and a conventional organic solvent, acetonitrile. Both polymers in acetonitrile and the zinc based DES (ZnCl2 / EG) satisfied the electro-neutrality condition through dominance of anion transfers. Whereas, polymers in the choline chloride based DES (Ethaline) satisfied the electro-neutrality condition through dominance of choline cation transfers (in the opposite direction to anion transfers). This research involved work towards the development of a new class of rechargeable batteries based on a Zinc-Polymer system incorporating a novel, inexpensive, environmentally sustainable solvent. This work is necessitated by the problems associated with petrol and diesel powered vehicles and the limitations of batteries available for electric vehicles.

Non-edible plant biomass (lignocellulose) is a valuable precursor for liquid biofuels, through the processes of pretreatment and saccharification followed by fermentation into products such as ethanol or butanol. However, it is difficult to gain access to the fermentable sugars in lignocellulose, and this problem is principally associated with limited enzyme accessibility. Hence, biomass pretreatments that destroy native cell wall structure and allows enzyme access are required for effective biomass conversion techniques. This research studied two novel pretreatment methods on two wood species: 1) a deep eutectic solvent (DES) that, under heat, swells lignocellulose and partially solubilizes cell wall materials by causing breakage of lignin-carbohydrate linkages and depolymerization of the biomass components, and 2) a chelator-mediated Fenton reaction (CMF) that chemically modifies the nanostructure of the cell wall through a non-enzymatic cell wall deconstruction. After pretreatment, utilizing analytical techniques such as nuclear magnetic spectroscopy, wide angle x-ray scattering, and gel permeation chromatography, samples were analyzed for chemical and structural changes in the solubilized and residual materials. After single stage DES (choline-chloride-glycerol) and two stage, CMF followed by DES pretreatments, lignin/carbohydrate fractions were recovered, leaving a cellulose-rich fraction with reduced lignin and hemicellulose content as determined by compositional analysis. Lignin and heteropolysaccharide removal by DES was quantified and the aromatic-rich solubilized biopolymer fragments were analyzed as water insoluble high molecular weight fractions and water-ethanol soluble low molecular weight compounds. After pretreatment for the hardwood sample, enzyme digestibility reached a saccharification yield of 78% (a 13-fold increase) for the two stage (DES/CMF) pretreated biomass even with the presence of some lignin and xylan remained on the pretreated fiber; only a 9-fold increase was observed after the other sequence of CMF followed by DES treatment. Single stage CMF treatment or single stage DES pretreatment improved 5-fold glucose yield compared to the untreated sample for the hardwood sample. The enhancement of enzymatic saccharification for softwood was less than that of hardwoods with only 4-fold increase for the sequence CMF followed by DES treatment. The other sequence of treatments reached up to 2.5-fold improvement. A similar result was determined for the single stage CMF treatment while the single stage DES treatment reached only 1.4-fold increase compared to the untreated softwood. Hence, all these pretreatments presented different degrees of biopolymer removal from the cell wall and subsequent digestibility levels; synergistic effects were observed for hardwood particularly in the sequence DES followed by CMF treatment while softwoods remained relatively recalcitrant. Overall, these studies revealed insight into two novel methods to enhance lignocellulosic digestibility of biomass adding to the methodology to deconstruct cell walls for fermentable sugars.<br>Ph. D.<br>Wood is a valuable material that can be used to produce liquid biofuels. Wood main components are biopolymers cellulose, hemicellulose and lignin that form a complex structure. Nature has locked up cellulose in a protective assembly that needs to be destroyed to gain access to cellulose, convert it to glucose and then ferment it to bioalcohol. This process is principally associated with limited enzyme accessibility. Therefore, biomass pretreatments that deconstruct native cell wall structure and allow enzyme access are required for effective biomass conversion techniques. This research studied two novel pretreatment methods on two wood species: 1) a deep eutectic solvent called glyceline that, under heat, swells wood and partially solubilizes cell wall materials by causing breakage of bonds and converting it into smaller molecules (monomers and oligomers), and 2) a chelator-mediated Fenton system (CMF) that chemically modifies the structure of the cell wall. Pretreatments were tested individually and in sequence in sweetgum and southern yellow pine. After pretreatments, utilizing analytical techniques, fractions were investigated for chemical and structural changes in the solubilized and residual materials. Treated wood samples were exposed to enzymatic conversion. A maximum 78% of glucose yield was obtained for the glyceline followed by CMF pretreated wood. For yellow pine only a 24% of glucose yield was obtained for the CMF followed by glyceline treatment. All these pretreatments presented different degrees of biopolymer removal from the cell wall and subsequent enzyme conversion levels. Overall, these studies revealed insight into two novel methods to enhance wood conversion adding to the methodology to deconstruct cell walls for fermentable sugars.

Interconnection layers fabricated during back end of line processing in semiconductor manufacturing involve dry etching of a low-k material and deposition of copper and metal barriers to create copper/dielectric stacks. After plasma etching steps used to form the trenches and vias in the dielectric, post etch residues (PER) that consist of organic polymer, metal oxides and fluorides, form on top of copper and low-k dielectric sidewalls. Currently, most semiconductor companies use semi aqueous fluoride (SAF) based formulations containing organic solvent(s) for PER removal. Unfortunately, these formulations adversely impact the environmental health and safety (EHS) requirements of the semiconductor industry. Environmentally friendly "green" formulations, free of organic solvents, are preferred as alternatives to remove PER. In this work, a novel low temperature molten salt system, referred as deep eutectic solvent (DES) has been explored as a back end of line cleaning (BEOL) formulation. Specifically, the DES system comprised of two benign chemicals, malonic acid (MA) and choline chloride (CC), is a liquid at room temperature. In certain cases, the formulation was modified by the addition of glacial acetic acid (HAc). Using these formulations, selective removal of three types of PER generated by timed CF₄/O₂ etching of DUV PR films on Cu was achieved. Type I PER was mostly organic in character (fluorocarbon polymer type) and had a measured thickness of 160 nm. Type II PER was much thinner (25 nm) and consisted of a mixture of organic and inorganic compounds (copper fluorides). Further etching generated 17 nm thick Type III PER composed of copper fluorides and oxides. Experiments were also conducted on patterned structures. Cleaning was performed by immersing samples in a temperature controlled (30 or 40° C) double jacketed vessel for a time between 1 and 5 minutes. Effectiveness of cleaning was characterized using SEM, XPS and single frequency impedance measurements. Type II and III residues, which contained copper compounds were removed in CC/MA DES within five minutes through dissolution and subsequent complexation of copper by malonic acid. Removal of Type I PER required the addition of glacial acetic acid to the DES formulation. Single frequency impedance measurement appears to be a good in situ method to follow the removal of the residues. High water solubility of the components of the system in conjunction with their environmental friendly nature, make the DES an attractive alternative to SAF.

Le développement de diverses applications utilisant l’hydrogène en tant que vecteur énergétique ouvre des voies prometteuses pour l'avenir. L’hydrogène peut être produit de différentes manières, l’une d’entre elles est l’électrolyse de l’eau et plus particulièrement sa réduction qui conduit à la production d’hydrogène (connue sous le nom de Hydrogen Evolution Reaction, HER). Cette technique nécessite l’emploi d’électrocatalyseurs performants. À l'heure actuelle, les catalyseurs à base d'alliages ou de composés de métaux nobles se distinguent par leur rendement électrocatalytique exceptionnel dans le cadre de la production d'hydrogène. Cependant, leur coût élevé et leurs réserves limitées compliquent leur utilisation à grande échelle dans l'industrie. C'est pourquoi il est impératif de concevoir et de développer de nouveaux matériaux permettant de produire de l'hydrogène économiques et respectueux de l'environnement. Ces dernières années, de nouveaux matériaux, notamment les alliages à base de métaux de transition tels que le nickel (Ni) et le cobalt (Co), ont été proposés et ont démontré d'excellentes propriétés catalytiques. Cependant, réduire davantage les coûts de préparation tout en améliorant les performances catalytiques et en respectant l'environnement s'avère être un défi de taille. C'est pourquoi, dans cette étude, nous mettrons l'accent sur la préparation d'alliages par électrodépôt, une méthode économique, et nous explorerons les effets de la composition élémentaire, de la structure de phase et de la morphologie de surface sur les performances électrocatalytiques. Au cours du processus d'électrodéposition, nous employons des électrolytes non conventionnels, communément désignés sous l'appellation de liquides ioniques. Comparativement aux solutions aqueuses, ces liquides ioniques présentent une teneur en eau considérablement moindre. Cette particularité sert à réduire la formation d'oxydes de métaux de transition. Par ailleurs, les liquides ioniques se caractérisent par une fenêtre électrochimique élargie, ce qui élargit notre éventail d'options en termes d'éléments d'alliage. Cette diversification nous autorise à scruter l'influence de divers éléments sur les performances de l'évolution de l'hydrogène, offrant ainsi des perspectives précieuses. De plus, la surface spécifique de l'électrocatalyseur joue un rôle central dans l'incidence sur les performances de la génération d'hydrogène. Une méthode connue sous l'appellation de désalliage est employée pour éliminer sélectivement une fraction des éléments d'alliage, ce qui conduit à la formation d'une structure nanoporeuse. Cette modification accroît davantage la surface spécifique du matériau. Nous avons mené avec succès l'électrodépôt d'alliages à base de Ni/Co dans des liquides ioniques ou des solvants eutectiques profonds (DES) en vue de préparer des électrocatalyseurs, puis nous les avons soumis à un traitement de surface par désalliage, fournissant ainsi de nouvelles informations sur le développement de matériaux pour la production d'hydrogène<br>The use of fossil energy, one of the main contributors to carbon emissions and a major source of pollution, has become a hot topic of discussion in recent years. Predicted energy shortages and the resulting environmental challenges are forcing mankind to look for alternatives to fossil fuels. Hydrogen is attracting increasing attention as a clean energy source, with high energy density and minimal emissions. It represents a promising, low-carbon energy carrier ready to supplant fossil fuels, particularly in the demanding industrial and transport sectors, where decarbonization is particular difficult to implement. According to existing literature, there are three main methods for producing hydrogen: hydrogen production from (i) fossil fuels, (ii) gasification, and (iii) water splitting. Water electrolysis under renewable resource conditions can practically eliminate carbon emissions, which is a significant difference compared to hydrogen production from fossil fuels (66 gCO2 e/MJ) or gasification (55 gCO2 e/MJ). Clearly, hydrogen production by electrolysis under ideal conditions has the distinct advantage of being environmentally friendly, with a low carbon footprint. Furthermore, water electrolysis offers many advantages, including the production of high-purity hydrogen, the simultaneous production of oxygen as a by-product, and simple installation. Although the hydrogen evolution reaction (HER) by water electrolysis provides numerous advantages for hydrogen production applications, its industrial adoption remains relatively limited, especially behind the production of hydrogen from fossil fuels. One of the main obstacles to its widespread use is the choice of electrocatalytic materials. Precious metals have exceptional electrocatalytic properties; however, their high cost and limited abundance on earth limit their practical application in all industries. Consequently, the search for cost-effective alternatives involving transition metals and the improvement of electrocatalyst performance through alloying and adjustments of surface morphology has emerged as important and dynamic lines of research. A wide range of techniques have been explored for synthesizing transition metal alloys used in electrocatalytic HER. Among these methods, electrodeposition stands out for its streamlined process, ease of implementation, and precise control, making it a versatile choice for large-scale applications. However, the hydrolysis of water during electrodeposition poses a problem. This can be effectively resolved by employing ionic liquids (ILs) as electrolytes, which are becoming increasingly popular due to their wide electrochemical window, high ionic conductivity, and user-friendly characteristics arising from their non-volatile and non-flammable nature. Surprisingly, research on the electrodeposition of alloys in ionic liquids remains relatively scarce. Consequently, combining the electrodeposition of alloy electrocatalysts with ionic liquids represents an attractive avenue to explore. In this work, we address the following questions: (1) Is it possible to prepare transition metal-based alloys by electrodeposition in ionic liquids? (2) What kinds of alloys can be prepared by electrodeposition in ionic liquids? (3) What is the impact of other elements (Co, Zn, Cu) on the HER properties of alloys? (4) How can the HER properties of alloys be enhanced by surface modification (dealloying)?

Abstract Nanocellulose is a renewable, biodegradable, and easily available material that is considered as an attractive resource for many different value-added applications in the emerging bio-based economy. Its outstanding properties, such as strength, lightness, transparency, and good thermal insulation, have inspired research and product development around nanocellulose. The potential of nanocellulose to replace synthetic chemicals made from non-renewable sources, for example, is considered to be very promising. Chemical functionalization, that is, the modification of the cellulosic surface properties, is seen to be beneficial in applications such as those in which higher hydrophobicity is needed. In this thesis, the ability of cellulose nanoparticles to stabilize oil droplets in oil-in-water emulsions was studied. The aim of the study was to explore the possibility of developing a new type of "green" oil spill chemical from cellulose. Therefore, the cellulose was chemically modified in an aquatic environment with a sequential periodate oxidation and chlorite oxidation followed by reductive amination reaction, which increased the hydrophobicity of the produced nanocellulose. In addition, the use of deep-eutectic solvents in the preparation of modified (succinylated and carboxylated) and non-modified cellulose nanoparticles was studied. Chemical (kraft) pulp, dissolving pulp, and semi-chemical fine fibers were used as raw materials in this research. The results demonstrated that chemically modified cellulose nanoparticles work well as stabilizers for oil-water emulsions resulting in small, stable oil droplets and impeding creaming, which is a typical phenomenon for particle stabilized emulsions. The modification of cellulose nanoparticles improved their ability to partition at the oil-water interface, which enabled efficient and irreversible adsorption. It was found that because of their small size, the cellulose nanocrystals can be compressed more tightly onto the surface of the oil droplet, while longer and more flexible cellulose nanofibrils formed a web structure between the oil droplets. All cellulose nanoparticle-stabilized emulsions were stable against droplet coalescence, and even at low temperatures, they retained their droplet size and stability. Salinity, on the other hand, improved stability when CNCs from chemical pulp were used, but it negatively affected stability when nanocrystals from semichemical pulp were used<br>Tiivistelmä Uusiutuva, biohajoava ja helposti saatavilla oleva nanoselluloosa on merkittävä tulevaisuuden raaka-aine useissa erilaisissa käyttökohteissa. Sen ylivertaiset ominaisuudet, kuten lujuus, keveys, läpinäkyvyys ja lämmöneristävyys ovat olleet innoittamassa nanoselluloosan tutkimusta ja tuotekehitystä. Nanoselluloosan mahdollisuuksia ja käyttöä eri sovelluksissa korvaamaan esimerkiksi uusiutumattomista luonnonvaroista valmistettuja kemikaaleja, pidetään erittäin lupaavina. Kemiallisesta funktionalisoinnista eli selluloosan pintaominaisuuksien muokkauksesta nähdään olevan hyötyä, kun tavoitellaan nanoselluloosan toiminnallisuutta esimerkiksi hydrofobista luonnetta vaativissa sovelluksissa pinta-aktiivisen aineen tavoin. Tässä työssä tutkittiin erityisesti nanoselluloosapartikkeleiden kykyä stabiloida öljypisaroita dieselöljy-vesiemulsioissa. Tutkimuksen päämääränä oli selvittää mahdollisuutta kehittää uudentyyppistä, ”vihreää” öljyntorjuntakemikaalia selluloosasta. Tämän vuoksi selluloosaa muokattiin kemiallisesti vesiympäristössä yhdistetyllä hapetus- ja aminointikäsittelyllä, mikä lisäsi valmistetun nanoselluloosan hydrofobisuutta. Toisena käsittelyvaihtoehtona tutkittiin syväeutektisten liuottimien käyttöä sekä muokattujen (sukkinyloidut ja karboksyloidut) että muokkaamattomien nanoselluloosapartikkeleiden valmistuksessa. Raaka-aineina työssä käytettiin kemiallista sellumassaa, liukosellua sekä puolikemiallista hienokuitua. Työn tuloksena voidaan todeta, että nanoselluloosasta valmistetut kemiallisesti muokatut (funktionalisoidut) nanopartikkelit toimivat hyvin öljy-vesiemulsiossa estäen emulsion öljypisaroiden yhteensulautumista. Nanopartikkelit stabiloivat emulsiossa olevan öljyn hyvin pieniksi pisaroiksi hidastaen kermottumista eli emulsion yleistä faasierottumista. Nanoselluloosan funktionalisointi paransi sen kykyä hakeutua öljy-vesi rajapintaan, mahdollistaen tehokkaan ja palautumattoman adsorption. Havaittiin, että pienen kokonsa vuoksi selluloosananokiteet pystyivät pakkautumaan tiiviimmin öljyn pinnalle, kun taas selluloosananokuidut, jotka ovat pidempiä, muodostivat verkkomaisen rakenteen myös öljypisaroiden väliin. Suolan lisäys vaikutti emulsion stabiilisuuteen vaihtelevasti eri näytteiden välillä, kun taas kylmät olosuhteet poikkeuksetta paransivat stabiilisuutta

博士<br>國立清華大學<br>化學工程學系<br>99<br>In this article, we demonstrate a new, facile and green antisolvent process to prepare nanostructure ZnO. The deep eutectic solvent (DES) is a new class green solvent that is negligible vapor pressure, high polar and biocompatible. UCC is one of DES that shows high solubility of many metal oxides that can be used as solvent in this approach. The antisolvent should be miscible with the DES UCC and non-solvent for the solute. By controlling the nucleation and growth, various morphologies of ZnO can be made by this method. At low ZnO concentration in UCC, ZnO twin-cone and rods can be prepared with morphology and size controls by injection rate and the ethanol content in antisolvent. The ethanol in the antisolvent can reduce the growth rate of ZnO and also lower the product dimensions. If the injection rate of ZnO-containing DES was reduced, the supply of Zn source became limited and the crystal growth became 1D dominated and grows on the preferred direction. It turns the product structure from twin-cones to nanorods. Mesocrystal ZnO is a mesoporous material fabricated from nanocrystals (NCs) with ordered orientation superstructure. Thus the material possesses high surface area and good crystallinity as single crystal. We use a biological buffer Tris as an oriented agent in antisolvent. ZnO NCs were made in antisolvent then Tris can increase the concentration of hydroxyl group in antisolvent. The hydroxyl group can attach on the oxygen vacancies on the polar O-terminated surface then increased the polarity of the ZnO NCs and then be attached together with the same orientation to form a mesocrystal ZnO. The increasing amount of Tris can make a larger size, better crystallinity and smaller surface area mesocrystal ZnO. The crystallinity is the more important factor rather than surface area. Thus a mesocrystal ZnO prepared in high Tris concentration shows better photocatalytic reactivity. At high ZnO dissolved concentration and low injection rate, the ZnO-ZCH nanosheet can be made by this antisolvent approach. After the annealing, single crystal mesoporous ZnO nanosheet can be parpared. The sheet is thin with a thickness of 10 nm and many pores with size of 5-60 nm can be found on the nanosheets. The ZnO nanosheet is single crystal and high surface area (~90 m2/g) with the exposed plane of (11-20). It can be used as photocatalyst for degradation of methylene blue (MB) in aqueous solution. The single crystal mesocrystal ZnO nanosheet shows performance as good as TiO2 P25.