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Andreas Hirsch

Publications and source records attributed to Andreas Hirsch.

30 records · Page 2Linked to original sources

Double- and Single-Sided bis-Functionalization of Graphene

For the first time bis-functionalization of graphene employing two successive reduction and covalent bond formation steps are reported. Both bulk functionalization in solution and functionalization of individual sheets deposited on surfaces have been carried out. Whereas in the former case attacks from both sides of the basal plane are possible and can lead to strain-free architectures, in the latter case, retro-functionalizations can get important when the corresponding anion of the addend represents a sufficiently good leaving group.

physics.chem-ph↗

Noncovalent Functionalization of Black Phosphorus

The first non-covalent functionalization of black phosphorus (BP) is presented. The treatment of BP with electron- withdrawing 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) leads to electron transfer from BP to the organic dopant. On the other hand, the non-covalent interaction of BP with perylene diimide is mainly due to van-der-Waals interactions but also leads to a considerable stabilization of the BP flakes against oxygen degradation.

physics.chem-ph↗

Substrate-Modulated Reductive Graphene Functionalization

Covalently functionalizing mechanical exfoliated monolayer and bilayer graphenides with λ-iodanes led to the discovery that the monolayers supported on a SiO2 substrate are considerably more reactive than bilayers as demonstrated by statistical Raman spectroscopy/microscopy. Supported by DFT calculations we show that ditopic addend binding leads to much more stable products than the corresponding monotopic reactions due to much lower lattice strain of the reactions products. The chemical nature of the substrate (graphene versus SiO2) plays a crucial role.14858-14862.

physics.chem-ph↗

Reductive Functionalization of Graphenides with Nickel(II) Porphyrin Diazonium Compounds

A novel type of a graphene/porphyrin hybrid with a direct covalent linker between graphene and a nickel(II) tetraphenylporphyrin unit has successfully been synthesized by the reductive exfoliation/functionalization of potassium intercalated graphite as starting material. Moreover, we directly compared the reactivity of two structurally different porphyrin derivatives, namely, meso-NiTPP-N2+, with the diazonium group in 4-position of a peripheral phenyl ring and a novel \b{eta} NiTPP N2+ diazonium cation, where the diazonium group is directly attached to the \b{eta}-pyrrolic position of the 18 π electron core. Due to sterical restraints, this intermediately generated porphyrin radical can not attack the extended π-surface of graphene and only a functionalization of present dangling bonds at the flake edges may be obtained in this case. All reaction products have been analyzed in detail be means of Raman- and UV/Vis spectroscopy as well as thermogravimetric analysis.

physics.chem-ph↗

Electronic and magnetic properties of black phosphorus

Black phosphorus has emerged as the next member in the graphene inspired two-dimensional materials family. Its electronic and magnetic properties are studied herein using electron and nuclear magnetic resonance techniques (ESR and NMR) and microwave conductivity measurement. The latter is a unique technique to study conductivity on air sensitive samples. The ESR study indicates the absence of free charge carriers and no sign of paramagnetic defects are found. $^{31}$P NMR shows the presence of a characteristic Pake doublet structure due to the interaction between $I = 1/2$ nuclei. Microwave conductivity shows, in accordance with the ESR results, that black phosphorus behaves as a semiconductor and we identify extrinsic and intrinsic charge carrier contributions to the conductivity and extracted the sizes of the gaps. ESR measurement also yields that bP might find applications as a microwave absorbent.

cond-mat.str-el↗

Perylene-Based Non-Covalent Functionalization of 2D Materials

The surfactant assisted exfoliation and non-covalent functionalization of two-dimensional layered materials, like graphene, transition metal dichalcogenides, etc., has extraordinarily been propelled forward within the last 5 years. Numerous molecules have been designed and attached to the exfoliated layers, and based on their outstanding properties, perylene based dyes have become one of the most frequently used π-detergents. Therefore, the prospect of this micro review is to summarize the most prominent achievements in this rapidly progressing field of research.

physics.chem-ph↗

Real-valued, time-periodic localized weak solutions for a semilinear wave equation with periodic potentials

We consider the semilinear wave equation $V(x) u_{tt} -u_{xx}+q(x)u = \pm f(x,u)$ for three different classes (P1), (P2), (P3) of periodic potentials $V,q$. (P1) consists of periodically extended delta-distributions, (P2) of periodic step potentials and (P3) contains certain periodic potentials $V,q\in H^r_{\per}(\R)$ for $r\in [1,3/2)$. Among other assumptions we suppose that $|f(x,s)|\leq c(1+ |s|^p)$ for some $c>0$ and $p>1$. In each class we can find suitable potentials that give rise to a critical exponent $p^\ast$ such that for $p\in (1,p^\ast)$ both in the "+" and the "-" case we can use variational methods to prove existence of time-periodic real-valued solutions that are localized in the space direction. The potentials are constructed explicitely in class (P1) and (P2) and are found by a recent result from inverse spectral theory in class (P3). The critical exponent $p^\ast$ depends on the regularity of $V, q$. Our result builds upon a Fourier expansion of the solution and a detailed analysis of the spectrum of the wave operator. In fact, it turns out that by a careful choice of the potentials and the spatial and temporal periods, the spectrum of the wave operator $V(x)\partial_t^2-\partial_x^2+q(x)$ (considered on suitable space of time-periodic functions) is bounded away from $0$. This allows to find weak solutions as critical points of a functional on a suitable Hilbert space and to apply tools for strongly indefinite variational problems.

math.AP↗

The First Precise Determination of Graphene Functionalisation by in situ Raman Spectroscopy

We report, for the first time, a comprehensive study involving in situ Raman spectroscopy supported by quantum mechanical calculations to exactly monitor the covalent binding to graphene with unprecedented precision. As a model reaction we have chosen the hydrogenation of reduced graphite ($KC_8$) with $H_2O$ and compared it with the corresponding exposure to $H_2$ and $O_2$. The early stages of graphene hydrogenation are accompanied by the evolution of a series of so far undiscovered D-bands ($D_1$-$D_5$). Using quantum mechanical calculations, we were able to unambiguously assign these bands to distinct lattice vibrations in the neighborhood of the covalently bound addend. Interestingly, the exposure of $KC_8$ to $H_2$ and $O_2$ didn't cause covalent binding, but intercalation of molecular $H_2$ or partial oxidation, respectively. A combination of $H_2O$ and $O_2$ treatment led to the formation of additional hydroxyl (-OH) functionalities. The latter reaction represents a very suitable model for the decomposition of graphenides under ambient conditions (hydrogenation and hydroxylation). We have applied this Raman analysis to simulate and satisfactorily characterize a series of additional covalently functionalised graphene derivatives prepared as bulk materials with different composition (e.g. degree of functionalisation and the nature of covalent addend) demonstrating the generality of the concept and the fundamental value for graphene chemistry.

cond-mat.mtrl-sci↗

Existence of cylindrically symmetric ground states to a nonlinear curl-curl equation with non-constant coefficients

We consider the nonlinear curl-curl problem $\nabla\times\nabla\times U + V(x) U=f(x,|U|^2)U$ in $\mathbb{R}^3$ related to the nonlinear Maxwell equations with Kerr-type nonlinear material laws. We prove the existence of a symmetric ground-state type solution for a bounded, cylindrically symmetric coefficient $V$ and subcritical cylindrically symmetric nonlinearity $f$. The new existence result extends the class of problems for which ground-state type solutions are known. It is based on compactness properties of symmetric functions due to Lions, new rearrangement type inequalities from Brock and the recent extension of the Nehari-manifold technique by Szulkin and Weth.

math.AP↗

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↗

Transport, Magnetic and Vibrational Properties of Chemically Exfoliated Few Layer Graphene

We study the vibrational, magnetic and transport properties of Few Layer Graphene (FLG) using Raman and electron spin resonance spectroscopy and microwave conductivity measurements. FLG samples were produced using wet chemical exfoliation with different post-processing, namely ultrasound treatment, shear mixing, and magnetic stirring. Raman spectroscopy shows a low intensity D mode which attests a high sample quality. The G mode is present at $1580$ cm$^{-1}$ as expected for graphene. The 2D mode consists of 2 components with varying intensities among the different samples. This is assigned to the presence of single and few layer graphene in the samples. ESR spectroscopy shows a main line in all types of materials with a width of about $1$ mT and and a $g$-factor in the range of $2.005-2.010$. Paramagnetic defect centers with a uniaxial $g$-factor anisotropy are identified, which shows that these are related to the local sp$^2$ bonds of the material. All kinds of investigated FLGs have a temperature dependent resistance which is compatible with a small gap semiconductor. The difference in resistance is related to the different grain size of the samples.

cond-mat.mtrl-sci↗

Turbostratic graphitic microstructures: electronically decoupled multilayer graphene devices with robust high charge carrier mobility

Carbon nanomaterials continue to amaze scientists due to their exceptional physical properties. Recently there have been theoretical predictions and first reports on graphene multilayers, where, due to the rotation of the stacked layers, outstanding electronic properties are retained while the susceptibility to degradation and mechanical stress is strongly reduced due to the multilayer nature. Here we show that fully turbostratic multilayer graphitic microstructures combine the high charge carrier mobilities necessary for advanced electronic and spintronic devices with the robustness of graphitic structures. Structural characterization of disk-shaped graphitic microstructures using Raman spectroscopy and Transmission Electron Microscopy (TEM) reveals Moiré and diffraction patterns corroborating their turbostratic nature. Electronic transport characterization yields reproducible high mobilities > 105 cm^2(Vs)^(-1) independent of the disks thickness, which is a direct consequence of the electronic decoupling induced by the turbostratic stacking.

cond-mat.mtrl-sci↗