Due to the multi-tasking and miniaturization of electronic devices, faster heat transfer is required from the device to avoid the thermal failure. Die-attached polymer adhesives are used to bond the chips in electronic packaging. These adhesives have to hold strong mechanical, thermal, dielectric, and moisture resistant properties. As polymers are insulators, heat conductive particles are inserted in it to enhance the thermal flow with an attention that there would be no electrical conductivity as well as no reduction in dielectric strength. This thesis focuses on the characterization of polymer nanocomposites for thermal and electrical properties with experimental and computational tools. Platelet geometry of hexagonal boron nitride offers highly anisotropic properties. Therefore, their alignment and degree of orientation offers tunable properties in polymer nanocomposites for thermal, electrical, and mechanical properties. This thesis intends to model the anisotropic behavior of thermal and dielectric properties using finite element and molecular dynamics simulations as well as experimental validation.

No description available.

Contemporary diagnostics rely on expensive, time-consuming, and optically-limited mechanisms that prevent at-home point-of-care molecular diagnostics with the accuracy of laboratory tools and the convenience of affordability. In this Thesis, biosensing was explored with commercial two-dimensional (2D) materials which have been investigated extensively over the last two decades yielding a variety of sensor metrics for detecting biomolecules. 2D materials have intrinsic properties that depend on the quality of material and substrate surface being employed. Here, graphene/SiO2 and monolayer hexagonal boron nitride (hBN) capping layer on graphene/SiO2 field-effect transistors (FETs) were used. Until recently, monolayer hBN has not been commercially available at the wafer-scale and has been observed in the literature to augment the properties of graphene-based devices and better control of processing repeatability. The work in this Thesis combines biochemistry with the wafer-scale production and surface-dependent properties of graphene and monolayer hBN/graphene via a FET fabrication process circumventing the use of photoresist. This was done to avoid photoresist resin that may contaminate the transducer surface and contribute to repeatability issues when studying biochemistry with 2D materials. Briefly, surface engineering of graphene/SiO2 and hBN/graphene/SiO2 was done, and the transfer characteristics were measured as a function of either the concentration of protons, genes, or proteins. Compared to bare 2D materials, the pH sensitivity of the shift in Dirac voltage was enhanced to -99 mV/pH when using 8.6 nm of Al2O3 on hBN/graphene/SiO2 FET. Graphene devices were then engineered for sensing SARS-CoV-2 genome with a signal-to-noise ratio of 3 at 100 aM and a linearized sensitivity of +22 mV/molar decade of SARS-CoV-2 ribonucleic acid and a dynamic range of four orders of magnitude. This was done by conjugating single-stranded deoxyribonucleic acid to sub-percolation threshold gold nanofilms deposited directly on the graphene sensing mesa. Finally, the 2D devices were studied for detecting SARS-CoV-2 spike protein after being functionalized with rabbit immunoglobulin G (IgG) monoclonal antibody (mAb). Additionally, preliminary work was done regarding the partial reduction and fragmentation of anti-SARS-CoV-2 spike protein human mAb IgG in an approach to leverage gold-thiol chemistry for covalently bonding the IgG to the 2D sensing mesa. In summary, the utilization of wide- and zero-bandgap nanomaterials may have profound implications in augmenting molecular diagnosis and treatment of disease through economically decentralizing biosensing. / 2024-01-20T00:00:00Z

This work presents a step forward in the use of 2D layered materials (2DLM), specifically hexagonal boron nitride (h-BN), for the fabrication of memristors. In this study, we fabricate, characterize, and use h-BN based memristors with Ag/few-layer h-BN/Ag structure to implement a fully functioning artificial leaky integrate-and-fire neuron on hardware. The devices showed volatile resistive switching behavior with no electro-forming process required, with relatively low VSET and long endurance of beyond 1.5 million cycles. In addition, we present some of the failure mechanisms in these devices with some statistical analyses to understand the causes, as well as a statistical study of both cycle-to-cycle and device-to-device variabilities in 20 devices. Moreover, we study the use of these devices in implementing a functioning artificial leaky integrate-and-fire neuron similar to a biological neuron in the brain. We provide SPICE simulation as well as hardware implementation of the artificial neuron that are in full agreement, showing that our device could be used for such application. Additionally, we study the use of these devices as an activation function for spiking neural networks (SNNs) by providing a SPICE simulation of a fully trained network, where the artificial spiking neuron is connected to the output terminal of a crossbar array. The SPICE simulations provide a proof of concept for using h-BN based memristor for activation function for SNNs.

Formation of hexagonal boron nitride (h-BN) by carbothermic reduction of B2O3 under nitrogen atmosphere at 1500oC was investigated. Reaction products were subjected to powder X-ray diffraction analysis, chemical analysis and were examined by SEM. B4C was found to exist in the reaction products of the experiments in which h-BN formation was not complete. One of the aims of this study was to investigate the role of B4C in the carbothermic production of h-BN. For this purpose, conversion reaction of B4C into h-BN was studied. B4C used in these experiments was produced in the same conditions that h-BN was formed, but under argon atmosphere. It was found that formation of h-BN from B4C&ndash / B2O3 mixtures was slower than activated C&ndash / B2O3 mixtures. It was concluded that B4C is not a necessary intermediate product in the carbothermic production of h-BN. Some additives are known to catalytically affect the h-BN formation. The second aim of this study was to examine the catalytic effect of some alkaline earth metal oxides and carbonates, some transition metal oxides and cupric nitrate. It was found that addition of 10wt% CaCO3 into the B2O3+C mixture was optimum for increasing the rate and yield of h-BN formation and decreasing the B4C amount in the products and that the reaction was complete in 2 hours. CaCO3 was observed to be effective in increasing the rate and grain size of the formed h-BN. Addition of cupric nitrate together with CaCO3 provided a further increase in the size of the h-BN grains.

Orientadores: Abner de Siervo, Richard Landers / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-25T18:41:09Z (GMT). No. of bitstreams: 1 DeLima_LuisHenrique_D.pdf: 24142455 bytes, checksum: b13ea70fe8434614a9b9ec40d25b3770 (MD5) Previous issue date: 2014 / Resumo: Monocamadas sp2 de grafeno e nitreto de boro hexagonal (h-BN) têm atraído muita atenção devido ao descobrimento de importantes propriedades, por exemplo, alta resistência mecânica, boa condutividade térmica e excelente estabilidade química e térmica. Porém, enquanto o grafeno é um semicondutor de gap nulo com alta mobilidade dos portadores de carga; o h-BN é um isolante com um largo band gap. Além disso, quando estas monocamadas sp2 são obtidas na superfície de uma variedade de substratos, elas podem exibir superestruturas corrugadas com parâmetro de rede no plano da ordem de nanômetros. Estas superestruturas são importantes para o autoordenamento de moléculas, átomos ou aglomerados de átomos e também para a intercalação de partículas e átomos em posições específicas na interface entre a monocamada sp2 e o substrato. Nesta tese, realizou-se um estudo, básico e aplicado, de monocamadas sp2 de grafeno e h-BN obtidas sobre a superfície do SiC(0001) e do Rh(111), respectivamente. Do ponto de vista básico, foi aplicada a técnica de Difração de Fotoelétrons (XPD) para um estudo da estrutura atômica do grafeno obtido por aquecimento na superfície do SiC(0001) e para a camada de interface entre o grafeno e o SiC, denominada buffer layer (BL). Os resultados de XPD mostraram particularidades distintas na estrutura atômica dessas monocamadas, o que explicaria a diferen_ca na estrutura eletrônica entre a BL e o grafeno. Do ponto de vista aplicado, foi mostrada a viabilidade do nanotemplate de grafeno/BL/SiC(0001) para a obtenção de aglomerados de Co e subsequente estudo das suas propriedades magnéticas por Dicroísmo Circular Magnético de Raios X (XMCD). Os aglomerados de Co foram obtidos sobre a camada de grafeno e os resultados evidenciam uma possível interação cluster-cluster de longo alcance, com influência nas propriedades magnéticas das partículas. Foi investigada também a intercalação dos átomos de Co entre o grafeno e a BL, formando uma rede quase periódica de clusters 2D. O grafeno forma uma barreira de proteção contra oxidação, preservando o caráter metálico das partículas. A monocamada de h-BN sobre a superfície do Rh(111) foi utilizada para a implantação de átomos de Rb. Para a implantação, foi construída uma evaporadora de íons de Rb que permite acelera-los numa faixa de energia possível para penetrar a monocamada de h-BN. Imagens de STM mostraram que os átomos de Rb termalizam entre a monocamada de h-BN e a superfície do Rh(111) em posições especificas da superestrutura, formando o que se denominou de nanotent. A formação dos nanotents e dos defeitos de vacância gerados pelo choque dos íons é uma forma de funcionalização do h-BN, sendo estas estruturas possíveis pontos de ancoragem de moléculas, átomos ou clusters de átomos / Abstract: Graphene and hexagonal boron nitride (h-BN) sp2 monolayers have attracted much attention due the discoveries of their important properties, such as high mechanical strength, good thermal conductivity and excellent chemical and thermal stability. However, while graphene is a zero band gap semiconductor with high carrier mobility; h-BN is a wide band gap insulator. Furthermore, when these sp2 monolayers are obtained on the surface of a variety of substrates, they can exhibit corrugated superstructures with a few nanometers in-plane lattice constants. Such superstructures are important for the self-assembly of molecules, atoms or clusters of atoms and also for the intercalation of these structures at specific positions between the sp2 monolayer and the substrate. In this thesis, we performed a study, fundamental and applied, of sp2 monolayers of graphene and h-BN obtained on the surface of SiC(0001) and Rh(111), respectively. From a fundamental point of view, the Photoelectron Di_raction (XPD) technique was applied for the study of the atomic structure of graphene obtained by heating the surface of the SiC(0001) and for the interface layer between the SiC and graphene, named buffer layer (BL). The XPD results showed distinct peculiarities in the atomic structure of these monolayers, which would explain the difference in electronic structure between BL and graphene. From the applied point of view, it has shown the feasibility of graphene/BL/SiC(0001) nanotemplate to obtain Co clusters and subsequent study of their magnetic properties by X-ray Magnetic Circular Dichroism (XMCD). The Co clusters were obtained on the graphene layer and the results suggest a possible clustercluster long-range interaction, that has influence on the magnetic properties of the particles. It was also investigated the intercalation of Co atoms between graphene, forming a quasi-periodic lattice of 2D-clusters. Moreover, graphene acts as a barrier to oxidation, preserving the metallic character of the clusters. The h-BN monolayer on the surface of Rh(111) was used for the implantation of Rb atoms. For the implantation, it was constructed an evaporator that allows the acceleration of Rb ions to an energy that enables the penetration through the h-BN monolayer. STM images show that the Rb atoms thermalize between the h-BN monolayer and the surface of the Rh(111) at specific positions of the superstructure, forming what is called a \\nanotent\". The formation of the nanotents and the vacancy defects generated by the collision of the ions is a form to functionalize the h-BN, with these structures being possible points for the anchoring of molecules, atoms or clusters of atoms / Doutorado / Física / Doutor em Ciências

During neural activity, action potentials travel down axons, generating effective charge current pulses, which are central in neuron-to-neuron communication. Consequently, said current pulses generate associated magnetic fields with amplitudes on the order of picotesla (pT) and femtotesla (fT) and durations of 10’s of ms. Magnetoencephalography (MEG) is a technique used to measure the cortical magnetic fields associated with neural activity. MEG limitations include the inability to detect signals from deeper regions of the brain, the need to house the equipment in special magnetically shielded rooms to cancel out environmental noise, and the use of superconducting magnets, requiring cryogenic temperatures, bringing opportunities for new magnetic sensors to overcome these limitations and to further advance neuroscience. An extraordinary magnetoresistance (EMR) tunable graphene magnetometer could potentially achieve this goal. Its advantages are linear response at room temperature (RT), sensitivity enhancement owing to combination of geometric and Hall effects, microscale size to place the sensor closer to the source or macroscale size for large source area, and noise and sensitivity tailoring. The magnetic sensitivity of EMR sensors is, among others, strongly dependent on the charge mobility of the sensing graphene layer. Mechanisms affecting the carrier mobility in graphene monolayers include interactions between the substrate and graphene, such as electron-phonon scattering, charge impurities, and surface roughness. The present work reviews and proposes a material set for increasing graphene mobility, thus providing a pathway towards pT and fT detection. The successful fabrication of large-size magnetic sensors employing CVD graphene is described, as well as the fabrication of trilayer magnetic sensors employing mechanical exfoliation of h-BN and graphene. The magneto-transport response of CVD graphene Hall bar and EMR magnetic sensors is compared to that obtained in equivalent trilayer devices. The sensor response characteristics are reported, and a determination is provided for key performance parameters such as current and voltage sensitivity and magnetic resolution. These parameters crucially depend on the material's intrinsic properties. The Hall cross magnetic sensor here reported has a magnetic sensitivity of ~ 600 nanotesla (nT). We find that the attained sensitivity of the devices here reported is limited by contaminants on the graphene surface, which negatively impact carrier mobility and carrier density, and by high contact resistance of ~2.7 kΩ µm at the metallic contacts. Reducing the contact resistance to < 150 Ω µm and eliminating surface contamination, as discussed in this work, paves the way towards pT and ultimately fT sensitivity using these novel magnetic sensors. Finite element modeling (FEM) is used to simulate the sensor response, which agrees with experimental data with an error of less than 3%. This enables the prediction and optimization of the magnetic sensor performance as a function of material parameters and fabrication changes. Predictive studies indicate that an EMR magnetic sensor could attain a sensitivity of 1.9 nT/√Hz employing graphene with carrier mobilities of 180,000 cm²/Vs, carrier densities of 1.3×10¹¹ cm^-2 and a device contact resistance of 150 Ω µm. This sensitivity increments to 443 pT/√Hz if the mobility is 245,000 cm²/Vs, carrier density is 1.6×10¹⁰ cm^-2, and a lower contact resistance of 30 Ω µm. Such devices could readily be deployed in wearable devices to detect biomagnetic signals originating from the human heart and skeletal muscles and for developing advanced human-machine interfaces.

The development of metals that can overcome the strength-ductility-weight trade-off has been an ongoing challenge in engineering for many decades. A promising option for making such materials are Metal matrix composites (MMCs). MMCs contain dispersions of reinforcement in the form of fibers, particles, or platelets that significantly improve their thermal, electrical, or mechanical performance. This dissertation focuses on reinforcement with two-dimensional (2D) materials due to their unprecedented mechanical properties. For instance, compared to steel, the most well-studied 2D material, graphene, is nearly forty times stronger (130 GPa) and five times stiffer (1 TPa). Examples of reinforcement by graphene have achieved increases in strength of 60% due to load transfer at the metal/graphene interface and dislocation blocking by the graphene. However, the superior mechanical properties of graphene are not fully transferred to the matrix in conventional MMCs, a phenomenon known as the "valley of death." In an effort to develop key insight into how the relationships between composite design, processing, structure, properties, and mechanics can be used to more effectively transfer the intrinsic mechanical properties of reinforcements to bulk composite materials, nanolayered composite systems made of Ni, Cu, and NiTi reinforced with graphene or 2D hexagonal boron nitride h-BN is studied using experimental techniques and molecular dynamics (MD) simulations. / Doctor of Philosophy / The design of new metals with concurrently improved strength and ductility has been an enduring goal in engineering for many decades. The utilization of components made with these new materials would reduce the weight of structures without sacrificing their performance. Such materials have the potential to revolutionize many industries, from electronics to aerospace. Traditional methods of improving the properties of metals by thermomechanical processing have approached a point where only minor performance improvements can be achieved. The development of Metal matrix composites (MMCs) is among the best approaches to achieving the strength-ductility goal. Metal matrix composites are a class of materials containing reinforcements of dissimilar materials that significantly improve their thermal conductivity, electrical conductivity, or mechanical performance. Reinforcements are typically in the form of dispersed fibers, particles, or platelets. The ideal reinforcement materials have superior mechanical properties compared to the metal matrix, a high surface area, and a strong interfacial bond with the matrix. Two-dimensional (2D) materials (materials made up of a single to a few layers of ordered atoms) are attractive for reinforcement in composite materials because they possess unprecedented intrinsic properties. The most well-studied 2D material, graphene, is made of a single layer of carbon atoms arranged in a hexagonal honeycomb pattern. It is nearly forty times stronger (130 GPa) and five times stiffer (1 TPa) than steel. Examples of graphene reinforcing have shown increases in strength of 60% due to load transfer at the metal/graphene interface and dislocation blocking by the graphene. Despite their exceptional mechanical properties, the superior mechanical properties of graphene are not fully transferred to the matrix when incorporated into conventional metal matrix composites. This phenomenon, known as the "valley of death," refers to the loss of mechanical performance at different length scales. One cause of this phenomenon is the difficulty of evenly dispersing the reinforcements in the matrix using traditional fabrication techniques. Another is the presence of dislocations in the metal matrix, which cause very large local lattice strains in the graphene. This atomistic-scale deformation at the interface between the metal and the graphene can significantly weaken it, leading to failure at low strains before reaching its intrinsic failure stress and strain. This dissertation aims to provide insight into how the relationships between composites' design, processing, structure, properties, and mechanics can be used to transfer intrinsic mechanical properties of reinforcements to bulk composite materials more effectively. For this, nanolayered composite systems of Ni and Cu reinforced with graphene or 2D h-BN were studied using experimental techniques and molecular dynamics (MD) simulations to elucidate the underlying mechanisms behind the composites' material structure and mechanical behavior. Additionally, we explore the incorporation of graphene in a metallic matrix that does not deform through dislocations (or shear bands), such as the shape memory alloy nickel-titanium ( Nitinol or NiTi), to avoid low strain failure of the metal/graphene interface. This theoretical strengthening mechanism is investigated by designing and fabricating NiTi/graphene composites.

This thesis explores the application of two-dimensional (2D) materials such as graphene and single layer hexagonal boron nitride (h-BN) which are produced by liquid phase exfoliation for use in printed electronics and energy composite applications. In Chapter 2 I give a broad overview of the electrical, mechanical and optical properties of 2D materials among other nanomaterials that were used in the thesis such as carbon nanotubes and conductive polymers. Additionally I review the techniques and theory behind the exfoliation and dispersion of functional layered materials. In Chapter 3 I present the coating and printing techniques which were used in this thesis along with the experimental techniques and methods which I use to characterise my inks, films and devices. Chapter 4 is the first experimental chapter of the thesis and demonstrates the printing of 2D material heterostructures to create fully printed dieletrically gated field effect transistors with 2D materials on textile and polymer substrates. In this chapter I also demonstrate reprogrammable volatile memory, p and n type inverters, complementary inverters, and logic gates which pave the way to fully printed integrated circuits, operational at room temperature and pressure with 2D materials processed in liquid. In Chapter 5, I review spray coating (a highly industrial scalable printing technique), in terms of the optimisation of its parameters to achieve thin films of nanomaterials on three-dimensional (3D) surfaces. I then demonstrate that it is possible to create large area (∼750 cm2) transparent conducting films around curved surfaces with spray coating enabling a semi-transparent (around 360°) spherical touch sensor for interactive devices. Chapter 6 explores printed photonics for applications in terahertz (THz) frequencies. Here I demonstrate the feasibility of liquid phase exfoliated graphene to create THz saturable absorbers (SAs) which could enable many applications in THz frequencies such as tomography or time-resolved spectroscopy that require mode-locked (i.e. enabling a train of short pulses to be derived from continuous-wave operation) THz pulses. I also demonstrate that these SAs can be inkjet printed on demand providing unprecedented compactness in a quantum cascade laser system. Finally in Chapter 7, I look at the application of graphene in microbial fuel cells (MFC). I demonstrate that enhanced MFC output arises from the interplay of the improved surface area, enhanced conductivity, and catalytic surface groups of a graphene based electrode. As a final step graphene based anodes and cathodes which were entirely platinum free were combined to create an environmentally sustainable energy source.

Boron nitride (BN) materials have unique properties, which has led to interest in them in the last few years. The deformation of boron nitride materials including hexagonal boron nitride, boron nitride nanosheets (BNNSs) and boron nitride nanotubes have been studied by Raman spectroscopy. Both mechanical and liquid exfoliations were employed to obtain boron nitride nanostructures. Boron nitride glass composites were synthesised and prepared in thin films to be deformed by bending test in-situ Raman spectroscopy. Hexagonal boron nitride in the form of an individual flake and as flakes dispersed in glass matrices has been deformed and Raman measurement shows its response to strain. The shift rates were, -4.2 cm-1/%, -6.5 cm-1/% for exfoliated h-BN flake with thick and thin regions and -7.0 cm-1/%, -2.8 cm-1/% for the h-BN flakes in the h-BN/ glass (I) and glass (II) composites. Boron nitride nanosheets (BNNSs) shows a G band Raman peak at 1367.5 cm-1, and the deformation process of BNNSs/ glass composites gives a shift rate of -7.65 cm-1/% for G band. Boron nitride nanotubes (BNNTs) have a Raman peak with position at 1368 cm-1, and their deformation individually and in composites gives Raman band shift rates of -25.7 cm-1/% and -23.6 cm-1/%. Glass matrices shows compressive stresses on boron nitride fillers and this was found as an upshift in the frequencies of G band peak of boron nitride materials. Grüneisen parameters of boron nitride (BN) were used to calculate the residual strains in glass matrices of BNNSs nanocomposites as well as to estimate the band shift rates which found to be in agreement with the experimental shift rate of bulk BN and BNNTs.