Electron paramagnetic resonance studies of nitrogen interstitial defects in diamond

We report on electron paramagnetic resonance (EPR) studies of nitrogen doped diamond that has been N-15 enriched, electron irradiated and annealed. EPR spectra from two new nitrogen containing S = 1/2 defects are detected and labelled WAR9 and WAR10. We show that the properties of these defects are consistent with them being the < 001 >-nitrogen split interstitial and the < 001 >-nitrogen split interstitial-< 001 >-carbon split interstitial pair, respectively. We also provide an explanation for why these defects have previously eluded discovery.

Hyperfine interaction in the ground state of the negatively charged nitrogen vacancy center in diamond

The N-14, N-15, and C-13 hyperfine interactions in the ground state of the negatively charged nitrogen vacancy (NV-) center have been investigated using electron-paramagnetic-resonance spectroscopy. The previously published parameters for the N-14 hyperfine interaction do not produce a satisfactory fit to the experimental NV- electron-paramagnetic-resonance data. The small anisotropic component of the NV- hyperfine interaction can be explained from dipolar interaction between the nitrogen nucleus and the unpaired-electron probability density localized on the three carbon atoms neighboring the vacancy. Optical spin polarization of the NV- ground state was used to enhance the electron-paramagnetic-resonance sensitivity enabling detailed study of the hyperfine interaction with C-13 neighbors. The data confirmed the identification of three equivalent carbon nearest neighbors but indicated the next largest C-13 interaction is with six, rather than as previously assumed three, equivalent neighboring carbon atoms.

Single crystal CVD diamond growth strategy by the use of a 3D geometrical model: Growth on (113) oriented substrates

The quality of single crystal diamond obtained by microwave CVD processes has been drastically improved in the last 5 years thanks to surface pretreatment of the substrates [A. Tallaire, J. Achard, F. Silva, R.S. Sussmann, A. Gicquel, E. Rzepka, Physica Status Solidi (A) 201, 2419-2424 (2004); G. Bogdan, M. Nesladek, J. D'Haen, J. Maes, V.V. Moshchalkov, K. Haenen, M. D'Olieslaeger, Physica Status Solidi (A) 202, 2066-2072 (2005); M. Yamamoto, T. Teraji, T. Ito, Journal of Crystal Growth 285, 130-136 (2005)]. Additionally, recent results have unambiguously shown the occurrence of (110) faces on crystal edges and (113) faces on crystal corners [F. Silva, J. Achard, X. Bonnin, A. Michau, A. Tallaire, O. Brinza, A. Gicquel, Physica Status Solidi (A) 203, 3049-3055 (2006)]. We have developed a 3D geometrical growth model to account for the final crystal morphology. The basic parameters of this growth model are the relative displacement speeds of (111), (110) and (113) faces normalized to that of the (100) faces, respectively alpha, beta, and gamma. This model predicts both the final equilibrium shape of the crystal (i.e. after infinite growth time) and the crystal morphology as a function of alpha, beta, gamma, and deposition time.

An optimized operating point, deduced from the model, has been validated experimentally by measuring the growth rate in (100), (111), (110), and (113) orientations. Furthermore, the evolution of alpha, beta, gamma as a function of methane concentration in the gas discharge has been established. From these results, crystal growth strategies can be proposed in order, for example, to enlarge the deposition area. In particular, we will show, using the growth model, that the only possibility to significantly increase the deposition area is, for our growth conditions, to use a (113) oriented substrate. A comparison between the grown crystal and the model results will be discussed and characterizations of the grown film (Photoluminescence spectroscopy, EPR, SEM) will be presented. (C) 2008 Elsevier B.V. All rights reserved.

Electron paramagnetic resonance studies of the neutral nitrogen vacancy in diamond

Despite the numerous experimental and theoretical studies on the negatively charged nitrogen vacancy center (NV-) in diamond and the predictions that the neutral nitrogen vacancy center (NV0) should have an S=1/2 ground state, NV0 has not previously been detected by electron paramagnetic resonance (EPR). We report new EPR data on a trigonal nitrogen-containing defect in diamond with an S=3/2 excited state populated via optical excitation. Analysis of the spin Hamiltonian parameters and the wavelength dependence of the optical excitation leads to assignment of this S=3/2 state to the (4)A(2) excited state of NV0. This identification, together with an examination of the electronic structure of the NV centers in diamond, provides a plausible explanation for the lack of observation (to date) of an EPR signal from the NV0 ground state.

Interstitial Nitrogen in Diamond – Optical and EPR Studies

Nitrogen is one of the most common impurities in diamond. On a substitutional site it acts as a deep donor, approximately 1.7 eV below the conduction band. Irradiation of nitrogen containing diamond and subsequent annealing creates the nitrogen vacancy centre, which has recently attracted much attention for quantum information processing application. Another possible product of irradiation and annealing of nitrogen containing diamond is interstitial nitrogen. Presumably, a mobile carbon interstitial migrates to a substitutional nitrogen to produce an interstitial nitrogen complex which may or may not be mobile. The configuration(s) of interstitial nitrogen related defects (e.g. bond centred, [001]-split) are not known. An infra-red (IR) absorption peak at 1450 cm-1 labelled H1a has been associated with an nitrogen interstitial complex. [1] Theoretical modelling suggested that this IR local mode is due to a bond centred nitrogen interstitial [2]. However, more recent modelling [3] suggests that this defect is mobile at temperatures were H1a is stable and instead assign H1a to two nitrogen atoms occupying a single lattice site in a [001]-split configuration. To date no electron paramagnetic resonance (EPR) spectra have been conclusively associated with an interstitial nitrogen defect.

In this study we present data from new EPR and optical absorption studies in combination with uniaxial stress of nitrogen interstitial related defects in electron irradiated and annealed nitrogen doped diamond. These measurements yield symmetry information about the defects allowing us to determine which of the proposed models are possible. EPR spectra of nitrogen interstitial related defects in samples isotopically enriched with 15N are reported and we show that these explain the lack of previous EPR data for these defects. Correlations between the IR absorbance and the integrated intensity of the new EPR defects are studied for varying irradiation doses and annealing temperatures.

Comparative performances of birnessite and cryptomelane MnO as electrode material in neutral aqueous lithium salt for supercapacitor application

Na-doped Birnessite-type manganese oxide (d-MnO) has been synthesized using the chemical method and characterized through X-ray diffraction and SEM, showing the lamellar structure and high crystal structure. A comparative study of the electrochemical performances of this material with those of the commercial Cryptomelane-type MnO has then been undertaken in ten neutral aqueous electrolytes for supercapacitor applications. Aqueous electrolytes, containing a lithium salt, LiX (where X = SO , NO, CHCO , CHSO, ClO , CHCO, TFSI, Beti, BOB, or Lact), have been first prepared under neutral pH conditions to reach the salt concentration, providing the maximum in conductivity. Their transport properties are then investigated through conductivities, viscosities, and self-diffusion coefficient measurements. Second, the thermal behaviors of these electrolytic aqueous solutions are then evaluated by using a differential scanning calorimeter from (213.15 to 473.15) K in order to access their liquid range temperatures. Cyclic voltammograms (CV) in three electrode configurations are thereafter investigated using Na Birnessite and Cryptomelane as working electrode material from (-0.05 to 1.5) V versus Ag/AgCl at various sweep rates from (2 to 100) mV·s. According to anion nature/structure and manganese oxide material type, different CV responses are observed, presenting a pure capacitive profile for Beti or CH CO and an additional pseudocapacitive signal for the smallest anions, such as ClO and NO . The capacitances, energies, and efficiencies are finally calculated. These results indicate clearly that electrolytes based on a mineral lithium salt under neutral pH condition and high salt concentration (up to 5 mol·L) have better electrochemical performances than organic ones, up to 1.4 V with good material stability and capacity retention. The relationship between transport properties, electrostatic and steric hindrance considerations of hydrated ions, and their electrochemical performances is discussed in order to understand further the lithium intercalation-deintercalation processes in the lamellar or tunnel structure of investigated MnO. © 2013 American Chemical Society.

Molecular dynamics simulation model for the quantitative assessment of tool wear during single point diamond turning of cubic silicon carbide

Silicon carbide (SiC) is a material of great technological interest for engineering applications concerning hostile environments where silicon-based components cannot work (beyond 623 K). Single point diamond turning (SPDT) has remained a superior and viable method to harness process efficiency and freeform shapes on this harder material. However, it is extremely difficult to machine this ceramic consistently in the ductile regime due to sudden and rapid tool wear. It thus becomes non trivial to develop an accurate understanding of tool wear mechanism during SPDT of SiC in order to identify measures to suppress wear to minimize operational cost.

In this paper, molecular dynamics (MD) simulation has been deployed with a realistic analytical bond order potential (ABOP) formalism based potential energy function to understand tool wear mechanism during single point diamond turning of SiC. The most significant result was obtained using the radial distribution function which suggests graphitization of diamond tool during the machining process. This phenomenon occurs due to the abrasive processes between these two ultra hard materials. The abrasive action results in locally high temperature which compounds with the massive cutting forces leading to sp3–sp2 order–disorder transition of diamond tool. This represents the root cause of tool wear during SPDT operation of cubic SiC. Further testing led to the development of a novel method for quantitative assessment of the progression of diamond tool wear from MD simulations.

Brittle-ductile transition during diamond turning of single crystal silicon carbide

In this experimental study, diamond turning of single crystal 6H-SiC was performed at a cutting speed of 1 m/s on an ultra-precision diamond turning machine (Moore Nanotech 350 UPL) to elucidate the microscopic origin of ductile-regime machining. Distilled water (pH value 7) was used as a preferred coolant during the course of machining in order to improve the tribological performance. A high magnification scanning electron microscope (SEM FIB- FEI Quanta 3D FEG) was used to examine the cutting tool before and after the machining. A surface finish of Ra=9.2 nm, better than any previously reported value on SiC was obtained. Also, tremendously high cutting resistance was offered by SiC resulting in the observation of significant wear marks on the cutting tool just after 1 km of cutting length. It was found out through a DXR Raman microscope that similar to other classical brittle materials (silicon, germanium, etc.) an occurrence of brittle-ductile transition is responsible for the ductile-regime machining of 6H-SiC. It has also been demonstrated that the structural phase transformations associated with the diamond turning of brittle materials which are normally considered as a prerequisite to ductile-regime machining, may not be observed during ductile-regime machining of polycrystalline materials.