Yes / 2D materials such as graphene, LAPONITE® clays or molybdenum disulfide nanosheets are of extremely high interest to the materials community as a result of their high surface area and controllable surface properties. While several methods to access 2D inorganic materials are known, the investigation of 2D organic nanomaterials is less well developed on account of the lack of ready synthetic accessibility. Crystallization-driven self-assembly (CDSA) has become a powerful method to access a wide range of complex but precisely-defined nanostructures. The preparation of 2D structures, however, particularly those aimed towards biomedical applications, is limited, with few offering biocompatible and biodegradable characteristics as well as control over self-assembly in two dimensions. Herein, in contrast to conventional self-assembly rules, we show that the solubility of polylactide (PLLA)-based amphiphiles in alcohols results in unprecedented shape selectivity based on unimer solubility. We use log Poct analysis to drive solvent selection for the formation of large uniform 2D diamond-shaped platelets, up to several microns in size, using long, soluble coronal blocks. By contrast, less soluble PLLA-containing block copolymers yield cylindrical micelles and mixed morphologies. The methods developed in this work provide a simple and consistently reproducible protocol for the preparation of well-defined 2D organic nanomaterials, whose size and morphology are expected to facilitate potential applications in drug delivery, tissue engineering and in nanocomposites. / University of Warwick, Materials GRP, EPSRC, The Royal Society, ERC

Yes / MXenes (viz., transition metal carbides, carbonitrides, and nitrides) have emerged as a new subclass of 2D materials. Due to their outstanding physicochemical and biological properties, MXenes have gained much attention in the biomedical field in recent years, including drug delivery systems, regenerative medicine, and biosensing. Additionally, the incorporation of MXenes into hydrogels has garnered significant interest in biomedical engineering as an electroactive and mechanical nanoreinforcer capable of converting nonconductive scaffolds into excellent conductors of electricity with an impressive effect on mechanical properties for the engineering of electroactive organs and tissues such as cardiac, skeletal muscle, and nerve. However, many questions and problems remain unresolved that need to be answered to usher these 2D materials toward their true destiny. Thus, this review paper aims to provide an overview of the design and applications of MXene-integrated composites for biomedical applications, including cardiac tissue engineering, wound healing, infection therapy, cancer therapy, and biosensors. Moreover, the current challenges and limitations of utilizing MXenes in vivo are highlighted and discussed, followed by its prospects as a guideline toward possible various futuristic biomedical applications. This review article will inspire researchers, who search for properties, opportunities, and challenges of using this 2D nanomaterial in biomedical applications. / Open Access Funding provided by Istituto Italiano di Tecnologia within the CRUI-CARE Agreement.

In this thesis, the effect of the sample properties on the characteristics of the hot carrier luminescence in graphene is investigated. The present work focuses on the two main issues described below. The first issue is the modification effects of near-infrared pulsed laser excitation on graphene. For excitation fluences several orders of magnitude lower than the optical damage threshold, the interaction with ultrafast laser pulses is found to cause a stable change in the properties of graphene. This photomodification also results in a decrease of the hot photoluminescence intensity. The detailed analysis shows that ultrafast photoexcitation leads to an increase in the local level of hole doping, as well as a change in the mechanical strain. The variation of doping and strain are linked with the enhanced adsorption of atmospheric oxygen caused by the distortion of the graphene surface. These findings demonstrate that ultrashort pulsed excitation can be invasive even if a relatively low laser power is used. Secondly, the variation of the hot photoluminescence intensity with the increasing charge carrier density in graphene is investigated. The electro-optical measurements performed using graphene field-effect transistors show a strong dependence of the photoluminescence intensity on the intrinsic carrier concentration. The emission intensity has a maximum value in undoped graphene and decreases with the increasing doping level. The theoretical calculations performed using a refined two-temperature model suggest that the reduction of the photoluminescence intensity is caused by an increase in the hot carrier relaxation rate. The modification of the carrier relaxation dynamics caused by photoinduced doping is probed directly using the two-pulse correlation measurements. The discovered sensitivity of the hot photoluminescence to the intrinsic carrier concentration can be utilised for spatially-resolved measurements of the Fermi level position in graphene samples, offering an advantage in resolution and speed.

Dynamic atomistic description of bio-inorganic interfaces represents a challenging problem for contemporary computational chemistry. A detailed analysis of processes occurring on the interface between biomolecule and inorganic material can help our understanding of various processes, ranging from chromatography and protein separation to protein immobilization techniques and their effect on enzyme activity or protein conformational stability. High complexity of bio- inorganic interfaces prevents detailed investigation using accurate, but computationally demanding ab initio methods. Since reliable empirical potentials are not available for these systems, the aim of this work is to develop force fields based on ab initio data as well as a general methodology for parameterization of such force fields. Our potential fitting procedure was carried out in an automated fashion based on molecular dynamics simulation. The resulting potentials were applied for investigation of inorganic material's influence on polypeptide conformations.

In this work, we study the properties and device applications of MoS2, black phosphorus, MoOx, and NbSe2. We first start with the design, fabrication, and characterization of ultra-high responsivity photodetectors based on mesoscopic multilayer MoS2. The device architecture is comprised of a metal-semiconductor-metal (MSM) photodetector, where Mo was used as the contact metal to suspended MoS2 membranes. The dominant photocurrent mechanism was determined to be the photoconductive effect, while a contribution from the photogating effect was also noted from trap-states that yielded a wide spectral photoresponse from UV-to-IR with an external quantum efficiency (EQE) ~ 104. From time-resolved photocurrent measurements, a fast decay time and response time were obtained with a stream of incoming ON/OFF white light pulses. Another interesting semiconductor 2D material that has attracted special attention due to its small bandgap and ultra-high hole mobility is the black phosphorus. An analysis of the optoelectronic properties and photocurrent generation mechanisms in two-dimensional (2D) multilayer crystallites of black phosphorus (BP) was conducted from 350 K down to cryogenic temperatures using a broad-band white light source. The Mo-BP interface yielded a low Schottky barrier "φ" _"SB" ~ -28.3 meV and a high photoresponsivity R of ~ 2.43 x 105 A/W at a source-drain bias voltage of ~ 0.5 V (300 K, and incident optical power ~ 3.16 μW/cm2). Our report is the first to highlight the empirical use of Mo as a contact metal with BP. From the analysis conducted on the BP devices, the thermally driven photocurrent generation mechanism arising from the photobolometric effect (PBE) dominated the carrier dynamics for T > 181 K since the photocurrent Iph and the bolometric coefficient β undergo a transition in polarity from positive to negative. Our results show the promise of BP to potentially advance thermoelectric and optoelectronic devices stemming from this mono-elemental, direct bandgap 2D van der Waals solid. Another intriguing metallic 2D material is superconducting 2H-NbSe2. Here we present the temperature-dependent Raman spectroscopy and electronic transport on bulk NbSe2, carried out to investigate the scattering mechanisms. We report on the photoresponse of direct probed mesoscopic 2H-NbSe2 as a function of laser energy for lasers at 405 nm, 660 nm, and 1060 nm wavelengths used to irradiate the device, where the modulation from the superconducting-to-normal-state is detected through photomodulation. Additionally, the various oxidation levels of molybdenum oxide have interesting optical and electrical properties as a function of the oxygen vacancy and stoichiometry. The substoichiometric MoOx (2 < x < 3) behaves as a high work function conductor due to its metallic defect band. As a result, one of the potential applications of MoOx is for electrical contacts providing high hole injection or extraction. In this work, we have synthesized MoOx nanosheets via chemical vapor deposition and a four-terminal device was fabricated via e-beam lithography and electronic transport was measured as a function of temperature. Outstanding properties were obtained from our MoOx nanosheets, including a high conductivity of ~ 6,680.3 S cm-1, a superior temperature coefficient of resistance ~ -0.10%, and a high sensitivity based on the bolometric coefficient β of ~ 0.152 mS K-1. In summary, this work pushes the state-of-the-art in enabling 2D van der Waals materials for next-generation high-performance detectors.

Les propriétés intrinsèques extraordinaires de ces matériaux de faible dimension dépendent fortement de l'environnement auquel ils sont soumis. Par conséquent, ils doivent être préparés, traités et caractérisés sans défauts. Dans cette thèse, je discute de la manière de contrôler l'environnement des nanomatériaux de faible dimension tels que le graphène, le MoS$_{2}$ et les nanotubes de carbone afin de préserver leurs propriétés physiques intrinsèques. De nouvelles solutions pour l'amélioration des propriétés sont discutées en profondeur. Dans la première partie, nous fabriquons des dispositifs d'hétérostructure à base de graphène de Van der Waals (VdW) de dernière génération, en contact avec les bords, encapsulés dans du nitrure de bore hexagonal (hBN), afin d'obtenir un transport balistique. Nous utilisons une technique basée sur des mesures de bruit 1 / f pour sonder le transport de masse et de bord lors de régimes Quantum Hall entiers et fractionnaires. Dans la deuxième partie, le même concept de fabrication des hétérostructures VdW a été étendu pour encapsuler la couche monocouche MoS $_{2}$ dans le hBN afin d'en modifier les propriétés optiques. À cet égard, nous présentons une étude approfondie sur l'origine et la caractérisation des défauts intrinsèques et extrinsèques et leur incidence sur les propriétés optiques. En outre, nous décrivons une technique pour sonder le couplage entre couches ainsi que la génération de lumière avec une résolution spatiale inférieure à la limite de diffraction de la lumière. Enfin, nous discutons d'un processus systémique naturel visant à améliorer les propriétés mécaniques de la soie polymérique naturelle à l'aide d'une nanotubes de carbone à paroi unique fabriqués par HipCO comme aliment pour le ver à soie. / The extraordinary intrinsic properties of low dimensional materials depend highly on the environment they are subjected to. Hence they need to be prepared, processed and characterized without defects. In this thesis, I discuss about how to control the environment of low dimensional nanomaterials such as graphene, MoS2 and carbon nanotubes to preserve their intrinsic physical properties. Novel solutions for property enhancements are discussed in depth. In the first part, we fabricate state-of-the-art, edge-contacted, graphene Van der Waals(VdW) heterostructuredevices encapsulated in hexagonal-boron nitride(hBN), to obtain ballistic transport. We use a technique based on 1/f-noise measurements to probe bulk and edge transport during integer and fractional Quantum Hall regimes. In the second part, the same fabrication concept of VdW heterostructures has been extended to encapsulate monolayer MoS2 in hBN to improve optical properties. In this regard we present an extensive study about the origin and characterization of intrinsic and extrinsic defects and their affect on optical properties. Further, we describe a technique to probe the interlayer coupling along with the generation of light with spatialresolution below the diffraction limit of light. Finally, we discuss a natural systemic process to enhance the mechanical properties of natural polymer silk using HipCO-made single walled carbon nanotubes as a food for silkworm.

Surface plasmons are collective oscillations of free electrons excited at a metal-dielectric interface by incident light. They possess a broad set of interesting properties including a high degree of tunability, the generation of strong field enhancements close to the metal's surface and high sensitivity to their adjacent dielectric environment. It is possible to enhance the sensitivity of plasmonic systems by using narrow plasmon resonances. In this thesis two approaches to narrowing surface plasmon resonances have been studied: diffraction coupling of localised surface plasmon resonances in gold nanoarrays and the use of graphene-protected copper thin films. Applications of these approaches in hybrid systems have been considered for modulation, waveguiding, biosensing and field enhancements. Arrays of gold nanostripes fabricated on a gold sublayer have been used to create extremely narrow plasmon resonances using diffraction coupling of localised plasmon resonances with quality factors up to a value of $Q \sim 300$, among the highest reported in the literature. The nanostructures were designed to give the narrowest resonance at the telecommunication wavelength of 1.5 µm, allowing for this array geometry to be used in hybrid systems for proof-of-concept optoelectronic devices. The gold nanostripe array was used in a hybrid nanomechanical electro-optical modulator along with hexagonal boron nitride (hBN) and graphene. The modulator was fabricated with an air gap between the nanoarray and the hexagonal boron nitride/graphene. Applying a gate voltage across the device moves the hBN towards the nanoarray, resulting in broadband modulation effects from the ultraviolet through to the mid-infrared dependant on the motion of the hBN instead of graphene gating. The deposition of a 400 nm hafnium(IV) oxide film on top of the gold nanoarray created a structure capable of guiding modes at 1.5 µm. The hybrid air-dielectric-stripe waveguide is capable of guiding modes over a distance of 250 µm. Copper thin films have stronger plasmon resonances and higher phase sensitivity than gold thin films. Transferring a graphene sheet on the copper prevents oxidation of the copper. A feasibility study of this hybrid system has shown that phase-sensitive graphene-protected copper biosensing can detect HT-2 mycotoxin with over four orders of magnitude greater sensitivity than commercially-available gold-based surface plasmon resonance biosensing systems. In summary, two methods of attaining narrow plasmon resonances have been demonstrated and their promise in modulation, waveguiding and biosensing have been demonstrated.

The production of large area, high quality two-dimensional (2D) materials using chemical vapour deposition (CVD) has been an important and difficult topic in contemporary materials science research, after the discovery of the diverse and extraordinary properties exhibited by these materials. This thesis mainly focuses on the CVD synthesis of two 2D materials; bilayer graphene and monolayer tungsten disulphide (WS2). Various factors influencing the growth of each material were studied in order to understand how they affect the quality, uniformity, and size of the 2D films produced. Following this, these materials were combined to fabricate 2D vertical heterostructures, which were then spectroscopically examined and characterised. By conducting ambient pressure CVD growth with a flat support, it was found that high uniform bilayer graphene could be grown on the centimetre scale. The flat support provides for the consistent delivery of precursor to the copper catalyst for graphene growth. These results provide important insights not only into the upscaling of CVD methods for growing large area, high quality graphene and but also in how to transfer the product onto flexible substrates for potential applications as a transparent conducting electrode. Monolayer WS2 is of interest for use in optoelectronic devices due to its direct bandgap and high photoluminescence (PL) intensity. This thesis shows how the controlled addition of hydrogen into the CVD growth of WS2 can lead to separately distributed domains or centimetre scale continuous monolayer films at ambient pressure without the need for seed molecules, specially prepared substrates or low pressure vacuum systems. This CVD reaction is simple and efficient, ideal for mass-production of large area monolayer WS2. Subsequent studies showed that hexagonal domains of monolayer WS2 can have discrete segmentation in their PL emission intensity, forming symmetric patterns with alternating bright and dark regions. Analysis of the PL spectra shows differences in the exciton to trion ratio, indicating variations in the exciton recombination dynamics. These results provide important insights into the spatially varying properties of these CVD-grown TMDs materials, which may be important for their effective implementation in fast photo sensors and optical switches. Finally, by introducing a novel non-aqueous transfer method, it was possible to create vertical stacks of mixed 2D layers containing a strained monolayer of WS2, boron nitride, and graphene. Stronger interactions between WS2 on graphene was found when swapping water for IPA, likely resulting from reduced contamination between the layers associated with aqueous impurities. This transfer method is suitable for layer by layer control of 2D material vertical stacks and is shown to be possible for all CVD grown samples, a result which opens up pathways for the rapid large scale fabrication of vertical heterostructure systems with large area coverage and controllable thickness on the atomic level.

Due to its truly two dimensional (2D) character and its particular lattice, single layer graphene (SLG) possesses exceptional properties: it is semimetallic, transparent, strong yet flexible ... Complementary features such as the insulating character of hexagonal boron nitride (h-BN) and semiconducting properties of transition metal dichalcogenides (TMDs) enable the whole spectrum of electronic devices to be built with combinations of these 2D materials. Due to this and the ease of exfoliation with a sticky tape, a vast amount of research was sparked. The mechanical exfoliation method, however, is only suitable for novel or proof-of-concept devices. The trend nowadays in electronics is towards transparent, lightweight, flexible, embedded smart devices and sensors in everyday objects such as windows and mirrors, garments, windshields, car seats, parachutes...These demands are already met inherently by these new materials, thus the challenges remaining are within their synthesis, deposition and processing, where more scalable ways of production and device fabrication need to be developed. This thesis explores innovative approaches using established techniques that aim to bridge the gap between proof-of-concept devices and real applications of 2D materials in future commercial level technologies. Methods to create graphene and engineer its properties are employed with a special focus on scalability and adaptability towards the industry. These graphene materials have been processed using pioneering schemes to create different optoelectronic devices and sensors. The techniques employed here for synthesis, transfer and deposition, device processing and characterization of graphene and derivatives, are suitable for their use in large manufacturing and mass-production. Depending on the application envisaged, different materials are used and optimize in order to balance good performance, cost-effectiveness and suitability/scalability of the process for the specific target the device was designed for.

The emerging 2D materials are potential solutions to the scaling of electronic devices to smaller sizes with lower energy cost and faster computing speed. Unlike traditional semiconductors e.g. Si, Ge, 2D materials do not have surface dangling bonds and the short-channel effect. A wide variety of band structure is available for different functions. The aim of the thesis is to calculate the electronic structures of several important 2D materials and study their application in particular devices, using density functional theory (DFT) which provides robust results. The Schottky barrier height (SBH) is calculated for hexagonal nitrides. The SBH has a linear relationship with metal work function but the slope does not always equal because Fermi level pinning (FLP) arises. The chemical trend of FLP is investigated. Then we show that the pinning factor of Si can be tuned by inserting an oxide interlayer, which is important in the application to dopant-free Si solar cells. Apart from contact resistance, we want to improve the conductivity of the electrode. This can be done by using a physisorbed contact layer like FeCl3, AuCl3, and SbF5 etc. to dope the graphene without making the graphene pucker so these dopants do not degrade the graphene's carrier mobility. Then we consider the defect formation of 2D HfS2 and SnS2 which are candidates in the n-type part of a tunnel FET. We found that these two materials have high mobility but there are also intrinsic defects including the S vacancy, S interstitial, and Hf/Sn interstitial. Finally, we study how to make defect states chemically inactive, namely passivation. The S vacancy is the most important defect in mechanically exfoliated 2D MoS2. We found that in the most successful superacid bis(trifluoromethane) sulfonamide (TFSI) treatment, H is the passivation agent. A symmetric adsorption geometry of 3H in the -1 charge state can remove all gap states and return the Fermi level to the midgap.