Trace element content and magnetic properties of commercial HOPG samples studied by ion beam microscopy and SQUID magnetometry

In this study, the impurity concentration and magnetic response of nine highly oriented pyrolytic graphite (HOPG) samples with different grades and from different providers were determined using ion beam microscopy and SQUID magnetometry. Apart from sideface contaminations in the as-received state, bulk contamination of the samples in most cases consists of disk-shaped micron-sized particles made of Ti and V with an additional Fe contamination around the grain perimeter. The saturation magnetization typically increases with Fe concentration, however, there is no simple correlation between Fe content and magnetic moment. The saturation magnetization of one, respectively six, out of nine samples clearly exceeds the maximum contribution from pure Fe or Fe3C. For most samples the temperature dependence of the remanence decreases linearly with T - a dependence found previously for defect-induced magnetism (DIM) in HOPG. We conclude that apart from magnetic impurities, additional contribution to the ferromagnetic magnetization exists in pristine HOPG in agreement with previous studies. A comparative study between the results of ion beam microscopy and the commonly used EDX analysis shows clearly that EDX is not a reliable method for quantitative trace elemental analysis in graphite, clarifying weaknesses and discrepancies in the element concentrations given in the recent literature.Comment: submitted to Carbo

Comment on: "Revealing common artifacts due to ferromagnetic inclusions in highly oriented pyrolytic graphite", by M. Sepioni, R.R. Nair, I.-Ling Tsai, A.K. Geim and I.V. Grigorieva, EPL 97 (2012) 47001

This comment addresses several issues in the paper by Sepioni et al., where it is stated that the ferromagnetism in pristine highly oriented pyrolytic graphite (HOPG) reported by several groups in the previous years is most likely due to impurity contamination. In this comment, clear arguments are given why this statement is not justified. Furthermore, it is pointed out, that there are already measurements using element-sensitive microscopic techniques, e.g. X-ray Magnetic Circular Dichroism (XMCD) that directly proved the intrinsic origin of the ferromagnetism in graphite, also in pristine HOPG.Comment: 1, 0 figures, 9 reference

π\pi-Electron Ferromagnetism in Metal Free Carbon Probed by Soft X-Ray Dichroism

Elemental carbon represents a fundamental building block of matter and the possibility of ferromagnetic order in carbon attracted widespread attention. However, the origin of magnetic order in such a light element is only poorly understood and has puzzled researchers. We present a spectromicroscopy study at room temperature of proton irradiated metal free carbon using the elemental and chemical specificity of x-ray magnetic circular dichroism (XMCD). We demonstrate that the magnetic order in the investigated system originates only from the carbon $\pi$-electron system.Comment: 10 pages 3 color figure

The role of hydrogen in room-temperature ferromagnetism at graphite surfaces

We present a x-ray dichroism study of graphite surfaces that addresses the origin and magnitude of ferromagnetism in metal-free carbon. We find that, in addition to carbon $\pi$ states, also hydrogen-mediated electronic states exhibit a net spin polarization with significant magnetic remanence at room temperature. The observed magnetism is restricted to the top $\approx$10 nm of the irradiated sample where the actual magnetization reaches $\simeq 15$ emu/g at room temperature. We prove that the ferromagnetism found in metal-free untreated graphite is intrinsic and has a similar origin as the one found in proton bombarded graphite.Comment: 10 pages, 5 figures, 1 table, submitted to New Journal of Physic

Experimental Evidence for Two-Dimensional Magnetic Order in Proton Bombarded Graphite

We have prepared magnetic graphite samples bombarded by protons at low temperatures and low fluences to attenuate the large thermal annealing produced during irradiation. An overall optimization of sample handling allowed us to find Curie temperatures $T_c \gtrsim 350$ K at the used fluences. The magnetization versus temperature shows unequivocally a linear dependence, which can be interpreted as due to excitations of spin waves in a two dimensional Heisenberg model with a weak uniaxial anisotropy.Comment: 4 pages, 3 figure

3D-Hydrogen Analysis of Ferromagnetic Microstructures in Proton Irradiated Graphite

Recently, magnetic order in highly oriented pyrolytic graphite (HOPG) induced by proton broad- and microbeam irradiation was discovered. Theoretical models propose that hydrogen could play a major role in the magnetism mechanism. We analysed the hydrogen distribution of pristine as well as irradiated HOPG samples, which were implanted to micrometer-sized spots as well as extended areas with various doses of 2.25 MeV protons at the Leipzig microprobe LIPSION. For this we used the sensitive 3D hydrogen microscopy system at the Munich microprobe SNAKE. The background hydrogen level in pristine HOPG is determined to be less than 0.3 at-ppm. About 4.8e15 H-atoms/cm^2 are observed in the near-surface region (4 um depth resolution). The depth profiles of the implants show hydrogen located within a confined peak at the end of range, in agreement with SRIM Monte Carlo simulations, and no evidence of diffusion broadening along the c-axis. At sample with microspots, up to 40 at-% of the implanted hydrogen is not detected, providing support for lateral hydrogen diffusion.Comment: accepted for publication in Nucl. Instr. and Met