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At least 181 records · Page 10

X-ray quantification of oxygen groups on diamond surfaces for quantum applications

Abstract Identifying the surface chemistry of diamond materials is increasingly important for device applications, especially quantum sensors. Oxygen-related termination species are widely used because they are naturally abundant, chemically stable, and compatible with stable nitrogen vacancy centres near the diamond surface. Diamond surfaces host a mixture of oxygen-related species, and the precise chemistry and relative coverage of different species can lead to dramatically different electronic properties, with direct consequences for near-surface quantum sensors. However, it is challenging to unambiguously identify the different groups or quantify the relative surface coverage. Here we show that a combination of x-ray absorption and photoelectron spectroscopies can be used to quantitatively identify the coverage of carbonyl functional groups on the { 100 } diamond surface. Using this method we reveal an unexpectedly high fraction of carbonyl groups ( > 9%) on a wide range of sample surfaces. Furthermore, through a combination of ab initio calculations and spectroscopic studies of engineered surfaces, we reveal unexpected complexities in the x-ray spectroscopy of oxygen terminated diamond surfaces. Of particular note, we find the binding energies of carbonyl-related groups on diamond differs significantly from other organic systems, likely resulting in previous misestimation of carbonyl fractions on diamond surfaces.

36 MATERIALS SCIENCE↗

Extreme Enhancement-Mode Operation Accumulation Channel Hydrogen-Terminated Diamond FETs with V th < -6 V and High on-Current

In this work, a new Field Effect Transistor device concept based on hydrogen-terminated diamond (H-diamond) is demonstrated that operates in an Accumulation Channel rather than a Transfer Doping regime. The FET devices demonstrate both extreme enhancement-mode operation and high on-current with improved channel charge mobility compared to Transfer-Doped equivalents. Electron-beam evaporated Al 2 O 3 is used on H-diamond to suppress the Transfer Doping mechanism and produce an extremely high ungated channel resistance. A high-quality H-diamond surface with an unpinned Fermi level is crucially achieved, allowing for the formation of a high-density hole accumulation layer by gating the entire device channel which is encapsulated in dual-stacks of Al 2 O 3 . Completed devices with gate/channel length of 1 µm demonstrate record threshold voltage < -6 V with on-current > 80 mA mm -1 . Carrier density and mobility figures extracted by CV analysis indicate a high 2D charge density of ≈ 2 × 10 12 cm -2 and increased hole mobility of 110 cm 2 V -1 s -1 in comparison with more traditional Transfer-Doped H-diamond FETs. These results demonstrate the most negative threshold voltage yet reported for H-diamond FETs and highlight a powerful new strategy to greatly improve carrier mobility and enable enhanced high power and high frequency diamond transistor performance.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Atomistic evidence of nucleation mechanism for the direct graphite-to-diamond transformation

The direct graphite-to-diamond transformation mechanism has been a subject of intense study and remains debated concerning the initial stages of the conversion, the intermediate phases, and their transformation pathways. Here, we successfully recover samples at the early conversion stage by tuning high-pressure/high-temperature conditions and reveal direct evidence supporting the nucleation-growth mechanism. Atomistic observations show that intermediate orthorhombic graphite phase mediates the growth of diamond nuclei. Furthermore, we observe that quenchable orthorhombic and rhombohedra graphite are stabilized in buckled graphite at lower temperatures. These intermediate phases are further converted into hexagonal and cubic diamond at higher temperatures following energetically favorable pathways in the order: graphite → orthorhombic graphite → hexagonal diamond, graphite → orthorhombic graphite → cubic diamond, graphite → rhombohedra graphite → cubic diamond. Furthermore, these results significantly improve our understanding of the transformation mechanism, enabling the synthesis of different high-quality forms of diamond from graphite.

Graphite-diamond phase transformation↗

Transient current induced in thin film diamonds by swift heavy ions

Single crystal diamond is a suitable material for the next generation particle detectors because of the superior electrical properties and the high radiation tolerance. In order to investigate charge transport properties of diamond particle detectors, transient currents generated in diamonds by single swift heavy ions (26 MeV O 5 + and 45 MeV Si 7 + ) are investigated. We also measured two dimensional maps of transient currents by single ion hits. In the case of 50 μm-thick diamond, both the signal height and the collected charge are reduced by the subsequent ion hits and the charge collection time is extended. Our results are thought to be attributable to the polarization effect in diamond and it appears only when the transient current is dominated by hole current. In the case of 6 μm-thick diamond membrane, an “island” structure is found in the 2D map of transient currents. Signals in the islands shows different applied bias dependence from signals in other regions, indicating different crystal and/or metal contact quality. Simulation study of transient currents based on the Shockley-Ramo theorem clarifies that accumulation of space charges changes distribution of electric field in diamond and causes the polarization effect.

36 MATERIALS SCIENCE↗

The transformation of diamond to graphite: Experiments reveal the presence of an intermediate linear carbon phase

Natural diamonds that have been partially replaced by graphite have been observed to occur in natural rocks. While the graphite-to-diamond phase transition has been extensively studied the opposite of this (diamond to graphite) remains poorly understood. We performed high-pressure and temperature hydrous and anhydrous experiments up to 1.0 GPa and 1300 °C using Amplex premium virgin synthetic diamonds (20–40 μm size) as the starting material mixed with Mg(OH) 2 as a source of H 2 O for the hydrous experiments. The experiments revealed that the diamond-to-graphite transformation at P = 1.0 GPa and T = 1300 °C was triggered by the presence of H 2 O and was accomplished through a three-stage process. Stage 1: diamond reacts with a supercritical H 2 O producing an intermediate 200–500 nm size “globular carbon” phase. This phase is a linear carbon chain; i.e. a polyyne or carbyne. Stage 2: the linear carbon chains are unstable and highly reactive, and they decompose by zigzagging and cross-linking to form sp 2 -hybridized structures. Stage 3: normal, disordered, and onion-like graphite is produced by the decomposition of the sp-hybridized carbon chains which are re-organized into sp 2 bonds. Our experiments show that there is no direct transformation from sp 3 C-bonds into sp 2 C-bonds. Our hydrous high-pressure and high-temperature experiments show that the diamond-to-graphite transformation requires an intermediate metastable phase of a linear hydrocarbon. This process also provides a simple mechanism for the substitution of other elements into the graphite structure (e.g. H, S, O).

36 MATERIALS SCIENCE↗

Nitrogen termination of single crystal (100) diamond surface by radio frequency N{sub 2} plasma process: An in-situ x-ray photoemission spectroscopy and secondary electron emission studies

In this letter, we report the electronic and chemical properties of nitrogen terminated (N-terminated) single crystal (100) diamond surface, which is a promising candidate for shallow NV{sup −} centers. N-termination is realized by an indirect RF nitrogen plasma process without inducing a large density of surface defects. Thermal stability and electronic property of N-terminated diamond surface are systematically investigated under well-controlled conditions by in-situ x-ray photoelectron spectroscopy and secondary electron emission. An increase in the low energy cut-off of the secondary electron energy distribution curve (EDC), with respect to a bare diamond surface, indicates a positive electron affinity of the N-terminated diamond. Exposure to atomic hydrogen results in reorganization of N-terminated diamond to H-terminated diamond, which exhibited a negative electron affinity surface. The change in intensity and spectral features of the secondary electron EDC of the N-terminated diamond is discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Hydrogen-terminated diamond vertical-type metal oxide semiconductor field-effect transistors with a trench gate

The hydrogen-terminated diamond surface (C-H diamond) has a two-dimensional hole gas (2DHG) layer independent of the crystal orientation. A 2DHG layer is ubiquitously formed on the C-H diamond surface covered by atomic-layer-deposited-Al{sub 2}O{sub 3}. Using Al{sub 2}O{sub 3} as a gate oxide, C-H diamond metal oxide semiconductor field-effect transistors (MOSFETs) operate in a trench gate structure where the diamond side-wall acts as a channel. MOSFETs with a side-wall channel exhibit equivalent performance to the lateral C-H diamond MOSFET without a side-wall channel. Here, a vertical-type MOSFET with a drain on the bottom is demonstrated in diamond with channel current modulation by the gate and pinch off.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

XPS analysis of molecular contamination and sp 2 amorphous carbon on oxidized (100) diamond

The efficacy of oxygen (O) surface terminations on diamond is an important factor for the performance and stability for diamond-based quantum sensors and electronics. Given the wide breadth of O-termination techniques, it can be difficult to discern which method would yield the highest and most consistent O coverage. Furthermore, the interpretation of surface characterization techniques is complicated by surface morphology and purity, which if not accounted for will yield inconsistent determination of the oxygen coverage. We present a comprehensive approach to consistently prepare and analyze oxygen termination of surfaces on (100) single-crystalline diamond. We report on x-ray photoelectron spectroscopy (XPS) characterization of diamond surfaces treated with six oxidation methods that include various wet chemical oxidation techniques, photochemical oxidation with UV illumination, and steam oxidation using atomic layer deposition (ALD). Our analysis entails a rigorous XPS peak-fitting procedure for measuring the functionalization of O-terminated diamond. The findings herein have provided molecular-level insights on oxidized surfaces in (100) diamond, including the demonstration of clear correlation between the measured oxygen atomic percentage and the presence of molecular contaminants containing nitrogen, silicon, and sulfur. We also provide a comparison of the sp 2 carbon content with the O1s atomic percentage and discern a correlation with the diamond samples treated with dry oxidation which eventually tapers off at a max O1s atomic percentage value of 7.09 ± 0.40%. Given these results, we conclude that the dry oxidation methods yield some of the highest oxygen amounts, with the ALD water vapor technique proving to be the cleanest technique out of all the oxidation methods explored in this work.

XPS↗

SU-F-T-570: Comparison of Synthetic Diamond, Microionization Chamber, and Radiochromic Film for Absolute Dosimetry of VMAT Radiosurgery

Purpose: Patient specific quality assurance of stereotactic radiosurgery (SRS) plans is challenging because of small target sizes and high dose gradients. We compared three detectors for dosimetry of VMAT SRS plans. Methods: The dose at the center of seventeen targets was measured using a synthetic diamond detector (2.2 mm diameter, 1 µm thickness), a 0.007 cm{sup 3} ionization chamber, and radiochromic film. Measurements were made in a PMMA phantom in the clinical geometry – all gantry and table angles were delivered as planned. The diamond and chamber positions were offset by 1 cm from the film plane, so the isocenter was shifted accordingly to place the center of the target at the detector of interest. To ensure accurate detector placement, the phantom was positioned using kV images. To account for the shift-induced difference in geometry and differing prescription doses between plans, the measurements were normalized to the expected dose calculated by the treatment planning system. Results: The target sizes ranged from 2.8 mm to 34.8 mm (median 14.8 mm). The mean measurement-to-plan ratios were 1.054, 1.076, and 1.023 for RCF, diamond, and chamber, respectively. The mean difference between the chamber and film was −3.2% and between diamond and film was 2.2%. For targets larger than 15 mm, the mean difference relative to film was −0.8% and 0.1% for chamber and diamond, respectively, whereas for targets smaller than 15 mm, the difference was −5.3% and 4.2% for chamber and diamond, respectively. The difference was significant (p=0.005) using the two-sample Kolmogorov-Smirnov test. Conclusion: The detectors agree for target sizes larger than 15 mm. Relative to film, for smaller targets the diamond detector over-responds, whereas the ionization chamber under-responds. Further work is needed to characterize detector response in modulated SRS fields.

60 APPLIED LIFE SCIENCES↗

Fast Scanning Diamond Detector for Electron Beam Profile Monitoring

The first prototype of a fast scanning diamond beam profile detector (DBPD) suitable for invasive high power CW electron beam core profile measurements in transmittance mode was developed. It consists of a multi-strip solid state diamond detector to scan with high speed (up to 1 m/s) and precision (about 5 μm) through the core of an electron beam. The diamond sensor was made from a thin polycrystalline diamond (PCD) plate with highly B-doped diamond conductive strips both grown by CVD. Transient currents from the multi-strip detector were measured with fast digitizing electrometers. Successful operation of the DBPD was demonstrated for pulsed (5 Hz) and CW (78 kHz) CeC beams, including the detector’s ability to withstand a 20 sec insertion into the CW CeC beam core. The X-Y beam spatial profile was measured in one scan. Thermal modelling demonstrated a manageable thermal impact even from a relatively long insertion of the diamond sensor into the CW CeC core and very short (0.2 s) insertion into the CW LEReC beam core. Electrical impedance modelling of the detector and vacuum chamber assembly demonstrated minimal impact on beam line impedance with diamond sensor insertion.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Coordinated Microstructural and Isotopic Characterization of Diamond Inclusions within the Kenna Ureilite

Introduction: The origin of diamonds in ureilitic meteorites, a major family of ultramafic achondrites, has long been debated, with various formation mechanisms inferred, including: 1) shock conversion of preexisting graphite due to a hypervelocity impact on the ureilite parent body [e.g., 1]; 2) vapor deposition during condensation of the solar nebula [e.g., 2]; or 3) static transformation in the mantle of a large planetesimal (>1000 km in diameter) [e.g., 3]. The Kenna ureilite is a 10.9 kg stone that was found in Kansas in 1972 and is dominantly composed of olivine and pigeonite (68% and 22% modal abundance, respectively), together with minor metal and carbon-rich regions. Within the carbon-rich domains researchers have identified microdiamonds up to ~10 µm in size [4]. Methods: Due to the proximity of the extremely hard microdiamonds with soft graphite and moderately hard silicates, achieving an appropriately flat surface for electron backscatter diffraction (EBSD) analysis has proven challenging. We have, therefore, employed a Hitachi ArBlade 5000 broad beam Ar ion milling system to prepare a sample with an adequately uniform surface flatness across the various minerals. The ion milling dramatically im-proved indexing of the EBSD patterns and facilitated high-resolution microstructural analysis of the carbon-rich domains. After microstructural EBSD analyses using an Oxford Symmetry detector we collected coordinated hy-perspectral cathodoluminescence (CL) analyses using a Gatan Monarc system mounted on a JEOL 7900F field emission (FE) scanning electron microscope at NASA Johnson Space Center. A focused ion beam (FIB) foil was extracted from a region of interest and analyzed using a JEOL 2500 FE scanning transmission electron microscope (STEM). In situ carbon and nitrogen isotopic analyses were collected from diamond-bearing domains using a Cameca NanoSIMS 50L at NASA JSC. Results: The carbon rich regions occur as tabular domains between polygonal olivine and pigeonite, and are composed of aggregates of micrometer-scale diamond with intermediate graphite, oxides and metal grains. Within the microdiamonds, {111} twins are abundant, many of which form ragged lamellae consistent with mechanical twinning. The microdiamond assemblages appear to pseudomorph tabular graphite habits, which together with the abundant deformation twins, support a shock transformation mechanism for microdiamond formation within the Kenna meteorite. Further supporting this observation, the diamond laths show close alignment of <111> and <110> between domains, consistent with a solid-state transformation from graphite along <0001> and <1-210>, respec-tively [5]. A FIB foil was extracted from a region with mechanical twins, and high resolution STEM analyses reveal cross-cutting veins of graphite and oriented kamacite crystals together with additional sets of {111} nano-twins formed in at least three orientations. Isotopic analyses of C and N reveal sector zoning patterns [cf. 3] that are unre-lated to the diamond substructure identified by EBSD yet consistent with hyperspectral CL images. Conclusions: These data provide new constraints on microdiamond formation within ureilites. The microdia-monds exhibit orientation variants defined by aligned <111> and <110> axes consistent with inherited crystallo-graphic orientations from transformation of a single hexagonal graphite parent crystal [5]. Crosscutting the micro-diamonds are veins of graphite and kamacite, together with additional {111} nanotwins. Taken together these data suggest that microdiamonds from ureilites formed from a solid state, diffusionless transformation from graphite, likely associated with a major shock event, which was subject to subsequent reversion either during decompression or a later deformation event. The N and C isotopic sector zoning is unrelated to diamond microstructures and likely reflects inheritance from the parent graphite crystal.

Ureilite↗

Subnanometer Thick Native sp 2 Carbon on Oxidized Diamond Surfaces

Oxygen-terminated diamond has a wide breadth of applications, which include stabilizing near-surface color centers, semiconductor devices, and biological sensors. Despite the vast literature on characterizing functionalization groups on diamond, the chemical composition of the shallowest portion of the surface (<1 nm) is challenging to probe with conventional techniques like XPS and FTIR. In this work, we demonstrate the use of angleresolved XPS to probe the first ten nanometers of both oxygen and hydrogen terminated (100) single-crystalline diamond grown via chemical vapor deposition (CVD). With the use of consistent peakfitting methods, the peak identities and relative peak binding energies were identified for sp 2 carbon, ether, hydroxyl, carbonyl, and C−H groups for both of these diamond surface terminations. For the oxygen-terminated sample, we also quantified the thickness of the sp 2 carbon layer situated on top of the bulk sp 3 diamond bonded carbon to be 0.3 ± 0.1 nm, based on the analysis of the Auger electron spectra and D-parameter calculations. These results indicate that the majority of the oxygen is bonded to the sp 2 carbon layer on the diamond, and not directly to the sp 3 diamond bonded carbon.

Carbon↗

Enhanced strength of nano-polycrystalline diamond by introducing boron carbide interlayers at the grain boundaries

Polycrystalline diamond with high mechanical properties and excellent thermal stability plays an important role in industry and materials science. However, the increased inherent brittle strength with the increase of hardness has severely limited its further widespread application. In this work, we produced well-sintered nano-polycrystalline (np) diamond by directly sintering fine diamond powders with the boron carbide (B 4 C) additive at high pressure and high temperatures. The highest hardness value of up to ~90 GPa was observed in the np-diamond (consisting of fine grains with a size of 16 nm) by adding 5 wt% B 4 C at 18 GPa and 2237 K. Moreover, our results reveal that the produced samples have shown noticeably enhanced strength and toughness (18.37 MPa m 0.5 ) with the assistance of the soft phase at the grain boundaries, higher than that of the hardest known nano-twined diamond by ~24% and a little greater than that of the toughest CVD diamond (18 MPa m 0.5 ). We report this study offers a novel functional approach in improving and controlling the hardness and stiffness of polycrystalline diamond.

36 MATERIALS SCIENCE↗

Stress engineering of high-quality single crystal diamond by heteroepitaxial lateral overgrowth

Here, we describe a method for lateral overgrowth of low-stress single crystal diamond by chemical vapor deposition (CVD). The process is initiated by deposition of a thin (550 nm) (001) diamond layer on Ir-buffered a-plane sapphire. The diamond is partially masked by periodic thermally evaporated Au stripes using photolithography. Lateral overgrowth of the Au occurs with extremely effective filtering of threading dislocations. Thermal stress resulting from mismatch of the low thermal expansion diamond and the sapphire substrate is largely accommodated by the ductile Au layer. The stress state of the diamond is investigated by Raman spectroscopy for two thicknesses: at 10 μm where the film has just overgrown the Au mask and at 180 μm where the film thickness greatly exceeds the scale of the masking. For the 10-μm film, the Raman linewidth shows spatial oscillations with the period of the Au stripes with a factor of 2 to 3 reduction relative to the unmasked region. In a 180-μm thick diamond film, the overall surface stress was extremely low, 0.00 ± 0.16 GPa, obtained from the Raman shift averaged over the 7.5mm diameter of the crystal at its surface. We conclude that the metal mask protects the overgrown diamond layer from substrate-induced thermal stress and cracking. Lastly, it is also responsible for low internal stress by reducing dislocation density by several orders of magnitude.

36 MATERIALS SCIENCE↗

Nitrogen and silicon defect incorporation during homoepitaxial CVD diamond growth on (111) surfaces

Chemical Vapor Deposited (CVD) diamond growth on (111)-diamond surfaces has received increased attention lately because of the use of N-V related centers in quantum computing as well as application of these defect centers in sensing nano-Tesla strength magnetic fields. We have carried out a detailed study of homoepitaxial diamond deposition on (111)-single crystal diamond (SCD) surfaces using a 1.2 kW microwave plasma CVD (MPCVD) system employing methane/hydrogen/nitrogen/oxygen gas phase chemistry. We have utilized Type Ib (111)-oriented single crystal diamonds as seed crystals in our study. The homoepitaxially grown diamond films were analyzed by Raman spectroscopy, Photoluminescence Spectroscopy (PL), X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). The nitrogen concentration in the plasma was carefully varied between 0 and 1500 ppm while a ppm level of silicon impurity is present in the plasma from the quartz bell jar. The concentration of N-V defect centers with PL zero phonon lines (ZPL) at 575nm and 637nm and the Si-defect center with a ZPL at 737nm were experimentally detected from a variation in CVD growth conditions and were quantitatively studied. As a result, altering nitrogen and oxygen concentration in the plasma was observed to directly affect N-V and Si-defect incorporation into the (111)-oriented diamond lattice and these findings are presented.

36 MATERIALS SCIENCE↗

Adsorptive Separation and Sequestration of Krypton, I and C14 on Diamond Nanoparticles

The objective of this research proposal was to address the separation and sequestration of Kr and I from each other using nano-sized diamond particles and retaining these in diamond until they decay to the background level or can be used as a byproduct. Following removal of Kr and I, an adsorbent will be used to adsorb and store CO 2 from the CO 2 rich stream. A Field Enhanced Diffusion with Optical Activation (FEDOA-a large scale process that takes advantage of thermal, electrical, and optical activation to enhance the diffusion of an element into diamond structure) was used to load Kr and I on micron or nano sized particles having a larger relative surface area. The diamond particles can be further increased by doping it with boron followed by irradiation in a neutron flux. Previous studies showed that the hydrogen storage capacity could be increased significantly by using boron-doped irradiated diamond particles. Diamond powders were irradiated for a longer time by placing them in a quartz tube. The surface area was measured using a Quantachrome Autosorb system. No significant increase in the surface area was observed. Total surface area was about 1.7 m 2 /g. This suggests the existence of very minimal pores. Interestingly it showed hysteresis upon desorption. A reason for this may be strong interaction between the surface and the nitrogen molecules. Adsorption runs at higher temperatures did not show any adsorption of krypton on diamond. Use of a GC with HID detector to determine the adsorption capacity from the breakthrough curves was attempted, but experimental difficulties were encountered.

36 MATERIALS SCIENCE↗

Hunting Sub-GeV Dark Matter with Diamonds and Magnetic Microcalorimeters Principle

This project is to study feasibility of a new concept for the sub-GeV dark matter (DM) detection using diamond crystals and magnetic microcalorimeters (MMCs). Diamond crystals are made of low mass carbon constituent that maximize kinetic energy of nuclear recoils from sub-GeV DM scattering due to their relatively similar masses. MMC is employed as a sensitive phonon sensor to measure athermal phonons that are produced by DM scattering in diamond crystals with 100 ns timing resolution and ~10 eV energy resolution. MMC’s fast timing resolution allows high precision phonon pulse shape analysis to separate out unwanted background or noise signals in the low energy region at E < 1 keV. Especially, the low energy excess (LEE) problems have been reported in the dark matter detection community and the proposed diamond-MMC detector might be able to provide important information to understand the origins of LEE signals in DM detectors. In this project a diamond-MMC detector has been built for proof-of-concept experiments and athermal phonon collection efficiencies have been investigated for single crystal and poly-crystal chemical-vapour-diamonds (SC and PC CVDs) as well as reference sapphire crystals are tested in the same geometries to quatify athermal phonon propagation and their collection to the MMC phonon sensors. Athermal phonon collection efficiencies and their lifetime in the diamond and sapphire crystals are successfully measured in the same geometry and experimental setup for comparison. SC CVD crystals exhibit poorer performance than the sapphire reference crystals in athermal phonon collection, while the PC CVD crystal exhibit better result than the sapphire. PC CVD with MMC phonon sensors would be feasible for sub GeV DM detection.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Carbon isotopic signatures of super-deep diamonds mediated by iron redox chemistry

Among redox sensitive elements, carbon is specifically important because it may have been a driver rather than a passive recorder of Earth’s redox evolution. The extent to which the isotopic composition of carbon records the redox processes that shaped the Earth is still debated. In particular, the highly reduced deep mantle may be metal-saturated, yet, it is still unclear how the presence of metallic phases influences the carbon isotopic compositions of super-deep diamonds. Here we report ab initio results for the vibrational properties of carbon in carbonates, diamond, and Fe 3 C under pressure and temperature conditions relevant to super-deep diamond formation. Previous work on this question neglected the effect of pressure on the equilibrium carbon isotopic fractionation between diamond and Fe 3 C but our calculations show that this assumption overestimates the fractionation by a factor of ~1.3. Our calculated probability density functions for the carbon isotopic compositions of super-deep diamonds derived from metallic melt can readily explain the very light carbon isotopic compositions observed in some super-deep diamonds. Our results therefore support the view that metallic phases are present during the formation of super-deep diamonds in the mantle below ~250 km.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗