Interrogation of nanostructured soft materials & interfaces from fundamental to emergent properties

The emergence of nanotechnology and nanoscience was largely due to the development of instruments that enabled sensing and manipulating materials at the nanoscale. Characterization at this scale is necessitated because nanostructured objects can exhibit drastically different properties than their bulk counterparts due to quantum effects and the increased importance of surface effects relative to bulk effects. The continuing trends of miniaturization spanning electronics, biology, and mechanics thus require that the state-of-the-art in nanomaterial characterization continues to advance in order to address the rapidly growing classes of nanomaterials and devices. In this dissertation, we present new approaches for characterizing soft materials and interfaces to address critical barriers facing their utilization, including throughput and performance. In our first study, we investigate the changes in mechanical properties of polymer nanoparticles that undergo a glass transition. Through a combination of mechanical (atomic force microscopy – AFM) and thermoanalytical (differential scanning calorimetry) methods, we observe the changes in glass transition temperature that derive from changes in particle size, absorbed water, and polymer molecular weight. We find that these polymer nanoparticles, chosen due to their ubiquitous use for drug delivery, can exhibit 50 fold lower elastic moduli under physiological conditions than they do in dry, ambient conditions as is commonly studied. This work concludes with a roadmap to allow experimentalists exploring nanoparticle mechanics to determine when direct nanoparticle indentation experiments are necessary. While the prior nanoindentation work was performed using commercial probes, these are limited in their bandwidth and ability to interrogate soft samples. To address the shortcomings of conventional indentation tools, in our next study, we explore the opportunities enabled by direct laser writing (DLW) to realize novel classes of AFM probes. Besides the capacity to image and interact with surfaces in a manner similar to conventional probes, DLW-written probes confer several useful advantages as result of their material composition and structural design flexibility, such as high-speed imaging and independent tuning of vibrational resonance modes. These results highlight the utility of tuning the structure of AFM probes in 3D and the ability to tailor individual probes using DLW without conventional wafer-scale batch processing. Lastly, to investigate surfaces with macroscale properties that emerge from the organization of matter on nanoscopic length scales, we develop a high-throughput platform for studying multifunctional surfaces capable of enzymatic activity and tunable wetting behavior. By patterning discrete domains that are uniformly functionalized, we demonstrate the co-optimization of functionalities that would otherwise be mutually exclusive. Variations in surface patterns enable optimization of the multifunctional surface by leveraging the different length scales that determine each functionality. The results presented here not only provide valuable insights regarding the co-optimization of enzymatic activity and hydrophobicity, but also show how high-throughput surface chemistry can impact our understanding and utilization of multifunctional surfaces more generally.2021-09-28T00:00:00

Effect of metal catalyst and tailoring the conditions for cnf/cnt growth through cvd

In this study, high-temperature acetylene gas was delivered to the reactive sites of matrix-supported transition metal catalysts by means of a chemical vapor deposition (CVD) apparatus, yielding carbon nanofibers (CNF) and nanotubes (CNT). A principle feature that delineated this pyrolysis-induced polymerization from prior studies lay in the method used to support the nanoscale transition metal catalysts. In particular, sodium chloride, a byproduct of the catalyst synthesis, was deliberately retained and exploited in subsequent manipulations for the reason that it performed remarkably well as a support medium. In comparison to typical silica and alumina-based support media, a non-porous sodium chloride medium clearly revealed major operational advantages in the matter of fabricating carbon species such as nanorods and nanotubes. In particular, pyrolysis could be conducted at temperatures spanning 500°C to 700°C without observing any agglomeration and subsequent sintering of the catalyst. The root cause of the high stability of these catalytic nanoparticles was not elucidated conclusively but it appeared to be related to the segregating effect of the support matrix, which could arise initially by the direct interaction between mobile chloride ions and the catalyst surface, and subsequently via encapsulation of each catalyst particle, by the growing polymeric species. The other noteworthy peculiarity of sodium chloride as a support material lay in its markedly different morphology, which could be characterized as microcrystalline and non-porous, with catalytic particles dispersed throughout the medium as opposed to remaining surface-pendent. While somewhat counter-intuitive, the zero-porosity of this matrix did not pose any apparent drawbacks in the matter of fabricating carbon nanofibers or nanotubes. In fact, the catalytic effectiveness of many transition metals particles was comparable or better than those of the prior art, whose effectiveness typically rests on utilizing a highly-porous and high-surface support medium with an interconnected morphology. High catalytic activity appeared to be promoted by the fact that the sodium chloride matrix became mobile and acetylene-permeable at elevated temperatures, the most important evidence originating from electron micrographs, which clearly indicated carbon-coated catalysts encased entirely in sodium chloride. In comparing several transition metal oxides, the most active catalyst was clearly nickel-based. The activity of the nickel catalyst did not appear to strongly depend on the ligand used in its fabrication but there was certainly a catalytic dependency on the size of the particle. Kinetic analyses of catalysts indicated that carbon-carbon bond formation was not reaction limited. Rather, the mass transfer of carbon units within the bulk or its chemisorption dynamics was in fact rate limiting, in agreement with literature studies on related systems. It followed to reason that the superior performance of nickel over other transition metal oxides was directly related to its stronger chemisorptivity of carbon species. Reaction rate versus flow rate measurements yielded a pseudo rate constant of zero for all catalyst types, implying that acetylene was saturating under the conditions of reaction. At prolonged reaction times, all catalysts lost their activity. While the possibility of catalyst poisoning could not be ruled out, other indications suggested that poor mass transfer of either the feedstock or the growing product were the likely cause. The morphology of carbon nanotubes were relatively typical whereas the morphology of nanofibers were subject to great variability, often ranging from straight rods to nanocoils to Y-junction or second order nanotubes on nanofiber structures. A hierarchy of the rules that governed the course of growth was not clearly established in this study but the major cause of this diversity appeared to be directly related to the shape, surface properties and the chemistry of the catalyst. Two other important parameters appeared to be the gas flow rate and the pyrolysis temperature. A final merit of employing the sodium chloride support technology was related to its preparative generality and practicality, particularly in view that it could enable the synthesis of metal catalysts and polymeric carbon species while precluding some common drawbacks such as toxicity, harsh experimental manipulations, and high cost. Even the quantitative recovery of catalyst could be facilitated by dissolution of the salt support in water, followed by filtration. It follows to reason that further development and fine-tuning of this novel and non-porous support technology can instigate a new class of support materials and can potentially open the door to the synthesis of carbon-based nanostructures with truly unusual physico-chemical traits

The Potential of Electrospinning to Enable the Realization of Energy-Autonomous Wearable Sensing Systems

The market for wearable electronic devices is experiencing significant growth and increasing potential for the future. Researchers worldwide are actively working to improve these devices, particularly in developing wearable electronics with balanced functionality and wearability for commercialization. Electrospinning, a technology that creates nano/microfiber-based membranes with high surface area, porosity, and favorable mechanical properties for human in vitro and in vivo applications using a broad range of materials, is proving to be a promising approach. Wearable electronic devices can use mechanical, thermal, evaporative and solar energy harvesting technologies to generate power for future energy needs, providing more options than traditional sources. This review offers a comprehensive analysis of how electrospinning technology can be used in energy-autonomous wearable wireless sensing systems. It provides an overview of the electrospinning technology, fundamental mechanisms, and applications in energy scavenging, human physiological signal sensing, energy storage, and antenna for data transmission. The review discusses combining wearable electronic technology and textile engineering to create superior wearable devices and increase future collaboration opportunities. Additionally, the challenges related to conducting appropriate testing for market-ready products using these devices are also discussed

Production and processing of graphene and related materials

© 2020 The Author(s). We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resourceconsuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown

Production and processing of graphene and related materials

© 2020 The Author(s). We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resourceconsuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown

Production and processing of graphene and related materials

We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV–VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resource-consuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown. Section VIII discusses advances in GRM functionalization. A broad range of organic molecules can be anchored to the sp2 basal plane by reductive functionalization. Negatively charged graphene can be prepared in liquid phase (e.g. via intercalation chemistry or electrochemically) and can react with electrophiles. This can be achieved both in dispersion or on substrate. The functional groups of GO can be further derivatized. Graphene can also be noncovalently functionalized, in particular with polycyclic aromatic hydrocarbons that assemble on the sp2 carbon network by π–π stacking. In the liquid phase, this can enhance the colloidal stability of SLG/FLG. Approaches to achieve noncovalent on-substrate functionalization are also discussed, which can chemically dope graphene. Research efforts to derivatize CNMs are also summarized, as well as novel routes to selectively address defect sites. In dispersion, edges are the most dominant defects and can be covalently modified. This enhances colloidal stability without modifying the graphene basal plane. Basal plane point defects can also be modified, passivated and healed in ultra-high vacuum. The decoration of graphene with metal nanoparticles (NPs) has also received considerable attention, as it allows to exploit synergistic effects between NPs and graphene. Decoration can be either achieved chemically or in the gas phase. All LMs, can be functionalized and we summarize emerging approaches to covalently and noncovalently functionalize MoS2 both in the liquid and on substrate. Section IX describes some of the most popular characterization techniques, ranging from optical detection to the measurement of the electronic structure. Microscopies play an important role, although macroscopic techniques are also used for the measurement of the properties of these materials and their devices. Raman spectroscopy is paramount for GRMs, while PL is more adequate for non-graphene LMs (see section IX.2). Liquid based methods result in flakes with different thicknesses and dimensions. The qualification of size and thickness can be achieved using imaging techniques, like scanning probe microscopy (SPM) or transmission electron microscopy (TEM) or spectroscopic techniques. Optical microscopy enables the detection of flakes on suitable surfaces as well as the measurement of optical properties. Characterization of exfoliated materials is essential to improve the GRM metrology for applications and quality control. For grown GRMs, SPM can be used to probe morphological properties, as well as to study growth mechanisms and quality of transfer. More generally, SPM combined with smart measurement protocols in various modes allows one to get obtain information on mechanical properties, surface potential, work functions, electrical properties, or effectiveness of functionalization. Some of the techniques described are suitable for 'in situ' characterization, and can be hosted within the growth chambers. If the diagnosis is made 'ex situ', consideration should be given to the preparation of the samples to avoid contamination. Occasionally cleaning methods have to be used prior to measurement

Synthesis and gas sensing properties of inorganic semiconducting, p-n heterojunction nanomaterials

En aquesta tesis utilitzant principalment Aerosol Assited Chemical Vapor Deposition, AACVD, com a metodologia de síntesis d'òxid de tungstè nanoestructurat s'han fabricat diferents sensors de gasos. Per tal d'estudiar la millora en la selectivitat i la sensibilitat dels sensors de gasos basats en òxid de tungstè aquest s'han decorat, via AACVD, amb nanopartícules d'altres òxids metàl·lics per a crear heterojuncions per tal d'obtenir un increment en la sensibilitat electrònica, les propietats químiques del material o bé ambdues. En particular, s'han treballat en diferents sensors de nanofils d'òxid de tungstè decorats amb nanopartícules d'òxid de níquel, òxid de cobalt i òxid d'iridi resultant en sensors amb un gran increment de resposta i selectivitat cap al sulfur d'hidrogen, per a l'amoníac i per a l'òxid de nitrogen respectivament a concentracions traça. A més a més, s'han estudiat els mecanismes de reacció que tenen lloc entre les espècies d'oxigen adsorbides a la superfície del sensor quan interactua amb un gas. I també s'ha treballat en intentar controlar el potencial de superfície de les capes nanoestructurades per tal de controlar la deriva en la senyal al llarg del temps, quan el sensor està operant, a través d'un control de temperatura.En esta tesis utilizando principalmente Aerosol Assited Chemical Vapor Deposition, AACVD, como metodología de síntesis de óxido de tungsteno nanoestructurado se han fabricado diferentes sensores de gases. Para estudiar la mejora en la selectividad y la sensibilidad de los sensores de gases basados en óxido de tungsteno estos se han decorado, vía AACVD, con nanopartículas de otros óxidos metálicos para crear heterouniones para obtener un incremento en la sensibilidad electrónica, las propiedades químicas del material o bien ambas. En particular, se han trabajado en diferentes sensores de nanohilos de óxido de tungsteno decorados con nanopartículas de óxido de níquel, óxido de cobalto y óxido de iridio resultante en sensores con un gran incremento de respuesta y selectividad hacia el sulfuro de hidrógeno, para el amoníaco y para el óxido de nitrógeno respectivamente a concentraciones traza. Además, se han estudiado los mecanismos de reacción que tienen lugar entre las especies de oxígeno adsorbidas en la superficie del sensor cuando interactúa con un gas. Y también se ha trabajado en intentar controlar el potencial de superficie de las capas nanoestructuradas para controlar la deriva en la señal a lo largo del tiempo, cuando el sensor está trabajando, a través de un control de temperatura.In this thesis, using mainly Aerosol Assited Chemical Vapor Deposition, AACVD, as a synthesis methodology for nanostructured tungsten oxide, different gas sensors have been manufactured. To study the improvement in the selectivity and sensitivity of gas sensors based on tungsten oxide, they have been decorated, via AACVD, with nanoparticles of other metal oxides to create heterojunctions to obtain an increase in electronic sensitivity, in the chemical properties of the material or at the same time in both. Particularly, we have worked on different tungsten oxide nanowire sensors decorated with nanoparticles of nickel oxide, cobalt oxide and iridium oxide resulting in sensors with a large increase in response and selectivity towards hydrogen sulfide, for ammonia. and for nitrogen oxide respectively at trace concentrations. In addition, the reaction mechanisms that take place between oxygen species adsorbed on the sensor surface when it interacts with a gas have been also studied. Furthermore, efforts have been put on trying to control the surface potential of the nanostructured layers to control the drift in the signal over time, when operating the sensors, through temperature control

Comparative spectroscopic characterization of fullerene nanomaterials

The higher fullerenes C76-D2 and C84-D2:22, as well as the basic fullerenes C60 and C70 were chromatographically isolated from carbon soot and the fullerol C60(OH)24 was synthesized, using new and advanced methods and processes. Their FT-IR(KBr) and electronic absorption spectra were recorded. All the observed infrared and UV/VIS bands are in excellent agreement with the theoretical calculations for these molecules. The molar absorptivity, as well as the integrated molar absorptivity of the absorption bands of the obtained fullerene nanomaterials was determined. These results are significant for their identification and quantitative determination either in natural resources or in artificially synthesized materials, electronic and optical devices, polymers, sensors, diagnostic and therapeutic agents, solar cells, nanophotonic lenses with optical absorption properties closer to human eye light sensitivity that can be used for early diagnosis of diabetes, in applied optical science, biomedical engineering and industry etc