arXiv subjects

Claudia Backes

Publications and source records attributed to Claudia Backes.

14 recordsLinked to original sources

arXiv2025

Toward All 2D-based Printed Raindrop Triboelectric Nanogenerators

The raindrop triboelectric nanogenerator (RD-TENG) is an emerging technology that is designed to harvest energy from raindrops. This application requires materials with negative triboelectric effect, high surface charge density, mechanical flexibility, and a large surface area, which are key characteristics of 2D materials. However, fundamental research is necessary to understand the potential of 2D materials in this context. This study introduces all-2D-based RD-TENG devices using graphene and transition metal dichalcogenide (TMD) nanosheets. Liquid phase exfoliation (LPE) and liquid cascade centrifugation are used for nanosheet preparation and size selection. The TENGs are fabricated through a rapid, low-cost solution deposition technique based on liquid-liquid interface deposition, which allows screening of different active films and device geometries. Among the tested layered materials, medium-sized molybdenum disulfide (MoS2) nanosheets (average lateral size~160 nm, volume-fraction weighted average layer number ~9) exhibit the highest short-circuit current (microampere per drop) and voltage (mV per drop) output due to their most suited electron affinity, capacitance, and surface charge exchange properties. The variations in the performance of the TMD films were further evaluated with X-ray photoelectron spectroscopy (XPS), showing the influence of oxidation differences on charge transfer and charge decay time.

physics.app-ph↗

arXiv2025

Centrifugation theory revisited: Understanding and modelling the centrifugation of 2D nanosheets

Size selection of liquid-dispersed 2D nanomaterials is a prerequisite for size-dependent studies in earlier stage research and for their targeted application in commercial settings. Centrifugation is the most widespread method for reliably sorting suspensions of polydisperse 2D nanosheets according to size. However, whilst centrifugation is effective, no a priori models are available to predict the outcome of centrifugation, making time consuming iterative experiments necessary. Here we present a simple model for the behaviour of 2D nanosheets during centrifugation and benchmark its predictions against experiments. This model uses simple expressions, specific to 2D particles, for the hydrodynamic radius, effective density and viscous resistance to generate the equation of motion of individual nanosheet during centrifugation. Critically, the equation of motion is then used to predict nanosheet size distributions within centrifugation products. This in turn leads to equations for easily measurable properties such as mean and maximum nanosheet sizes obtained during centrifugation-based fractionation. Comparison with experimental data demonstrates the robustness of this model for a range of 2D materials and solvent systems, and its ability to describe quite subtle effects. These results will enable more tailored size selection of nanosheets for specific applications and offer new mechanistic insights to optimise exfoliation conditions.

cond-mat.mes-hall↗

arXiv2024

Sonication-assisted liquid phase exfoliation of two-dimensional CrTe$_3$ under inert conditions

Liquid phase exfoliation (LPE) has been used for the successful fabrication of nanosheets from a large number of van der Waals materials. While this allows to study fundamental changes of material properties' associated with reduced dimensions, it also changes the chemistry of many materials due to a significant increase of the effective surface area, often accompanied with enhanced reactivity and accelerated oxidation. To prevent material decomposition, LPE and processing in inert atmosphere have been developed, which enables the preparation of pristine nanomaterials, and to systematically study compositional changes over time for different storage conditions. Here, we demonstrate the inert exfoliation of the oxidation-sensitive van der Waals crystal, CrTe$_3$. The pristine nanomaterial was purified and size-selected by centrifugation, nanosheet dimensions in the fractions quantified by atomic force microscopy and studied by Raman, X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDX) and photo spectroscopic measurements. We find a dependence of the relative intensities of the CrTe$_3$ Raman modes on the propagation direction of the incident light, which prevents a correlation of the Raman spectral profile to the nanosheet dimensions. XPS and EDX reveal that the contribution of surface oxides to the spectra is reduced after exfoliation compared to the bulk material. Further, the decomposition mechanism of the nanosheets was studied by time-dependent extinction measurements after water titration experiments to initially dry solvents, which suggest that water plays a significant role in the material decomposition.

cond-mat.mtrl-sci↗

arXiv2024

Algorithm for Reproducible Analysis of Semiconducting 2D Nanomaterials Based on UV/VIS Spectroscopy

Rapid and reliable analysis of liquid dispersions of 2D materials is essential for fully harnessing their potential, allowing size and quality validation before subsequent processing or device fabrication. Existing UV-VIS extinction spectroscopy-based metrics, particularly those related to thickness, have shown promise but rely on manual data processing, which can introduce irreproducibility and user errors. To address this challenge and enable uniform analysis across laboratories, a freely available program is developed for the reproducible analysis of nanosheet dispersions. Specifically, a smoothing routine is applied to the spectral data, takes the second derivative, and use integral areas to find the wavelength of exciton transitions. This program enables rapid measurement of nanosheet concentration, length, and thickness by UV-VIS spectroscopy and thickness metrics are refined for eight common 2D nanomaterials. The program and methodology are freely available for use and allow metrics for new materials to be implemented easily in the future.

cond-mat.mes-hall↗

arXiv2023

Solution-processed NiPS3 thin films from Liquid Exfoliated Inks with Long-Lived Spin-Entangled Excitons

Antiferromagnets are promising materials for future opto-spintronic applications since they show spin dynamics in the THz range and no net magnetization. Recently, layered van der Waals (vdW) antiferromagnets have been reported, which combine low-dimensional excitonic properties with complex spin-structure. While various methods for the fabrication of vdW 2D crystals exist, formation of large area and continuous thin films is challenging because of either limited scalability, synthetic complexity, or low opto-spintronic quality of the final material. Here, we fabricate centimeter-scale thin films of the van der Waals 2D antiferromagnetic material NiPS3, which we prepare using a crystal ink made from liquid phase exfoliation (LPE). We perform statistical atomic force microscopy (AFM) and scanning electron microscopy (SEM) to characterize and control the lateral size and number of layers through this ink-based fabrication. Using ultrafast optical spectroscopy at cryogenic temperatures, we resolve the dynamics of photoexcited excitons. We find antiferromagnetic spin arrangement and spin-entangled Zhang-Rice multiplet excitons with lifetimes in the nanosecond range, as well as ultranarrow emission linewidths, despite the disordered nature of our films. Thus, our findings demonstrate scalable thin-film fabrication of high-quality NiPS3, which is crucial for translating this 2D antiferromagnetic material into spintronic and nanoscale memory devices and further exploring its complex spin-light coupled states.

physics.chem-ph↗

arXiv2022

Photophysical comparison of liquid and mechanically exfoliated WS$_2$ monolayers

Semiconducting transition metal dichalcogenides (TMDs) are desired as active materials in optoelectronic devices due to their strong excitonic effects. They can be exfoliated from their parent layered materials with low-cost and for mass production via a liquid exfoliation method. However, the device application of TMDs prepared by liquid phase exfoliation is limited by their poor photoluminescence quantum efficiencies (PLQE). It is crucial to understand the reason to low PLQE for their practical device development. Here we evaluate the quality of monolayer-enriched liquid phase exfoliated (LPE) WS$_2$ dispersions by systematically investigating their optical and photophysical properties and contrasting with mechanically exfoliated (ME) WS2 monolayers. An in-depth understanding of the exciton dynamics is gained with ultrafast pump-probe measurements. We reveal that the energy transfer between monolayer and few-layers in LPE WS$_2$ dispersions is a substantial reason for their quenched PL. In addition, we show that LPE WS$_2$ is promising to build high performance optoelectronic devices with excellent optical quality.

physics.app-ph↗

arXiv2021

Thermal Transport in Graphene Composites: The Effect of Lateral Dimensions of Graphene Fillers

We report on the investigation of thermal transport in non-cured silicone composites with graphene fillers of different lateral dimensions. Graphene fillers are comprised of few-layer graphene flakes with lateral sizes in the range from 400 nm to 1200 nm and number of atomic planes from one to ~100. The distribution of the lateral dimensions and thicknesses of graphene fillers has been determined via atomic force microscopy statistics. It was found that in the examined range of the lateral dimensions the thermal conductivity of the composites increases with the increasing size of the graphene fillers. The observed difference in thermal properties can be related to the average gray phonon mean free path in graphene, which has been estimated to be around ~800 nm at room temperature. The thermal contact resistance of composites with graphene fillers of 1200-nm lateral dimensions was also smaller than that of composites with graphene fillers of 400-nm lateral dimensions. The effects of the filler loading fraction and the filler size on the thermal conductivity of the composites were rationalized within the Kanari model. The obtained results are important for optimization of graphene fillers for applications in thermal interface materials for heat removal from high-power-density electronics.

physics.app-ph↗

arXiv2020

Equipartition of Energy Defines the Size-Thickness Relationship in Liquid-Exfoliated Nanosheets

Liquid phase exfoliation is a commonly used method to produce 2D nanosheets from a range of layered crystals. However, such nanosheets display broad size and thickness distributions and correlations between area and thickness, issues that limit nanosheet application potential. To understand the factors controlling the exfoliation process, we have liquid-exfoliated 11 different layered materials, size-selecting each into fractions before using AFM to measure the nanosheet length, width, and thickness distributions for each fraction. The resultant data show a clear power-law scaling of nanosheet area with thickness for each material. We have developed a simple nonequilibrium thermodynamics-based model predicting that the power-law prefactor is proportional to both the ratios of in-plane-tearing/out-of-plane-peeling energies and in-plane/out-of-plane moduli. By comparing the experimental data with the modulus ratio calculated from first-principles, we find close agreement between experiment and theory. This supports our hypothesis that energy equipartition holds between nanosheet tearing and peeling during sonication-assisted exfoliation.

physics.chem-ph↗

arXiv2020

Spectroscopic thickness and quality metrics for PtSe$_2$ layers produced by top-down and bottom-up techniques

Thin films of noble-metal-based transition metal dichalcogenides, such as PtSe$_2$, have attracted increasing attention due to their interesting layer-number dependent properties and application potential. While it is difficult to cleave bulk crystals down to mono- and few-layers, a range of growth techniques have been established producing material of varying quality and layer number. However, to date, no reliable high-throughput characterization to assess layer number exists. Here, we use top-down liquid phase exfoliation (LPE) coupled with centrifugation to produce widely basal plane defect-free PtSe$_2$ nanosheets of varying sizes and thicknesses. Quantification of the lateral dimensions by statistical atomic force microscopy allows us to quantitatively link information contained in optical spectra to the dimensions. For LPE nanosheets we establish metrics for lateral size and layer number based on extinction spectroscopy. Further, we compare the Raman spectroscopic response of LPE nanosheets with micromechanically exfoliated PtSe$_2$, as well as thin films produced by a range of bottom up techniques. We demonstrate that the Eg1 peak position and the intensity ratio of the Eg1/ A1g1 peaks can serve as robust metric for layer number across all sample types and will be of importance in future benchmarking of PtSe$_2$ films.

physics.app-ph↗

arXiv2020

Defect Engineering of Two-dimensional Molybdenum Disulfide

Two-dimensional (2D) molybdenum disulfide (MoS2) holds great promise in electronic and optoelectronic applications owing to its unique structure and intriguing properties. The intrinsic defects such as sulfur vacancies (SVs) of MoS2 nanosheets are found to be detrimental to the device efficiency. To mitigate this problem, functionalization of 2D MoS2 using thiols has emerged as one of the key strategies for engineering defects. Herein, we demonstrate an approach to controllably engineer the SVs of chemically exfoliated MoS2 nanosheets using a series of substituted thiophenols in solution. The degree of functionalization can be tuned by varying the electron withdrawing strength of substituents in thiophenols. We find that the intensity of 2LA(M) peak normalized to A1g peak strongly correlates to the degree of functionalization. Our results provide a spectroscopic indicator to monitor and quantify the defect engineering process. This method of MoS2 defect functionalization in solution also benefits the further exploration of defect free MoS2 for a wide range of applications.

physics.chem-ph↗

arXiv2018

Spectroscopic size and thickness metrics for liquid-exfoliated h-BN

For many 2D materials, optical and Raman spectra are richly structured, and convey information on a range of parameters including nanosheet size and defect content. By contrast, the equivalent spectra for h-BN are relatively simple, with both the absorption and Raman spectra consisting of a single feature each, disclosing relatively little information. Here, the ability to size-select liquid-exfoliated h-BN nanosheets has allowed us to comprehensively study the dependence of h-BN optical spectra on nanosheet dimensions. We find the optical extinction coefficient spectrum to vary systematically with nanosheet lateral size due to the presence of light scattering. Conversely, once light scattering has been decoupled to give the optical absorbance spectra, we find the size dependence to be mostly removed save for a weak but well-defined variation in energy of peak absorbance with nanosheet thickness. This finding is corroborated by our ab initio GW and Bethe-Salpeter equation calculations, which include electron correlations and quasiparticle self-consistency (QSGW). In addition, while we find the position of the sole h-BN Raman line to be invariant with nanosheet dimensions, the linewidth appears to vary weakly with nanosheet thickness. These size-dependent spectroscopic properties can be used as metrics to estimate nanosheet thickness from spectroscopic data.

cond-mat.mes-hall↗

arXiv2017

Probing the local nature of excitons and plasmons in few-layer MoS2

Excitons and plasmons are the two most fundamental types of collective electronic excitations occurring in solids. Traditionally, they have been studied separately using bulk techniques that probe their average energetic structure over large spatial regions. However, as the dimensions of materials and devices continue to shrink, it becomes crucial to understand how these excitations depend on local variations in the crystal- and chemical structure on the atomic scale. Here we use monochromated low-loss scanning-transmission-electron-microscopy electron-energy-loss (LL-STEM-EEL) spectroscopy, providing the best simultaneous energy and spatial resolution achieved to-date to unravel the full set of electronic excitations in few-layer MoS2 nanosheets over a wide energy range. Using first-principles many-body calculations we confirm the excitonic nature of the peaks at ~2eV and ~3eV in the experimental EEL spectrum and the plasmonic nature of higher energy-loss peaks. We also rationalise the non-trivial dependence of the EEL spectrum on beam and sample geometry such as the number of atomic layers and distance to steps and edges. Moreover, we show that the excitonic features are dominated by the long wavelength (q=0) components of the probing field, while the plasmonic features are sensitive to a much broader range of q-vectors, indicating a qualitative difference in the spatial character of the two types of collective excitations. Our work provides a template protocol for mapping the local nature of electronic excitations that open new possibilities for studying photo-absorption and energy transfer processes on a nanometer scale.

cond-mat.mtrl-sci↗

arXiv2015

Understanding and optimising the packing density of perylene bisimide layers on CVD-grown graphene

The non-covalent functionalisation of graphene is an attractive strategy to alter the surface chemistry of graphene without damaging its superior electrical and mechanical properties. Using the facile method of aqueous-phase functionalisation on large-scale CVD-grown graphene, we investigated the formation of different packing densities in self-assembled monolayers (SAMs) of perylene bisimide derivatives and related this to the amount of substrate contamination. We were able to directly observe wet-chemically deposited SAMs in scanning tunnelling microscopy (STM) on transferred CVD graphene and revealed that the densely packed perylene ad-layers adsorb with the conjugated π-system of the core perpendicular to the graphene substrate. This elucidation of the non-covalent functionalisation of graphene has major implications on controlling its surface chemistry and opens new pathways for adaptable functionalisation in ambient conditions and on the large scale.

cond-mat.mes-hall↗

arXiv2015

Liquid exfoliation of solvent-stabilised black phosphorus: applications beyond electronics

Few layer black phosphorus is a new two-dimensional material which is of great interest for applications, mainly in electronics. However, its lack of stability severely limits our ability to synthesise and process this material. Here we demonstrate that high-quality, few-layer black phosphorus nanosheets can be produced in large quantities by liquid phase exfoliation in the solvent N-cyclohexyl-2-pyrrolidone (CHP). We can control nanosheet dimensions and have developed metrics to estimate both nanosheet size and thickness spectroscopically. When exfoliated in CHP, the nanosheets are remarkably stable unless water is intentionally introduced. Computational studies show the degradation to occur by reaction with water molecules only at the nanosheet edge, leading to the removal of phosphorus atoms and the formation of phosphine and phosphorous acid. We demonstrate that liquid exfoliated black phosphorus nanosheets are potentially useful in a range of applications from optical switches to gas sensors to fillers for composite reinforcement.

cond-mat.mes-hall↗