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At least 55 records · Page 3

The Petrography of Meteoritic Nano-Diamonds

At least some meteoritic nanodiamonds are likely of presolar origin because of their association with anomalous Xe-HL and Te isotopic components indicative of a supernova (SN) origin. But the abundance of Xe is such that only approx. 1 in 10(exp 6) nano-diamonds contains a Xe atom, and the bulk C-13/C-12 composition of nano-diamond acid residues is chondritic (solar). Therefore, it is possible that a significant fraction of meteoritic nano-diamonds formed within the solar nebula. Nano-diamonds have recently been detected for the first time within the accretion discs of young stars by the Infrared Space Observatory (ISO). No comparable evidence of nanodiamonds in the interstellar medium has yet been found. We have identified nano-diamonds in acid etched thin-sections of meteorites, polar micrometeorites, and interplanetary dust particles (IDPs) with the goal of determining their distribution as a function of heliocentric distance. (It is assumed the meteorites and the polar micrometeorites are from asteroids at 2-4 AU and at least some of the IDPs are from comets at >50AU). We found that nano-diamonds are heterogeneously distributed throughout carbon-rich meteoritic materials (we identified them in some IDPs and not in others), and that their abundance may actually decrease with heliocentric distance, consistent with the hypothesis that some of them formed within the inner solar system and not in a presolar (SN) environment. In order to gain further insight about the origins of meteoritic nano-diamonds we are currently investigating their distribution in unetched thin-sections. We have examined a chondritic cluster IDP (U220GCA), fragments of the Tagish Lake (CM1) meteorite, and a SN graphite spherule (KE3d8) isolated from the Murchison (CM) meteorite. We selected U220GCA because its nano-diamond abundance (in acid etched thin-sections) appears to be as much as approx. 10X higher than in Murchison matrix, Tagish Lake because it has a higher reported nano-diamond abundance than other carbonaceous chondrites (approx. 3650-4330 ppm), and KE3d8 because it is a carbon spherule with an isotopic composition suggesting that it is a bone fide presolar SN grain.

Dai, Z. R.↗

Triphasic Tooling with Small Oriented Diamond Tip for Turning and Smoothing Lightweight Mirrors

We are developing a new method for the growth of small diamond crystals at very high temperatures and pressures directly from a carbon melt. A prototype "Supercell" has been developed for this purpose. This system is capable of high rate crystal growth in relatively large working volumes. The resulting high quality diamond crystals will be incorporated into a triphasic diamond/titanium carbide/titanium composite tool, with an oriented diamond crystal at its tip. High pressure is needed to prevent degradation of diamond at high temperature, and to ensure the formation of a crack & composite structure. After grinding and polishing, the composite material will be joined to a steel holder, thus forming a diamond-tipped tool for turning and smoothing of a mirror surface. A properly oriented single-crystal diamond cuts and smoothes much better than a conventional polycrystalline diamond crystal. This is because the hardness depends on crystallographic orientation-the difference corresponds to 60-100 GPa on the Knoop scale. Our goal is to achieve surface roughness of about 1 nm, which will be accomplished by precision cutting and smoothing. The hardness of the functionally-graded diamond/titanium carbide/titanium composite tool varies from 100 GPa at its tip to 15 GPa at its base. Previous work has shown that the mass of machined material using an oriented-diamond tool is much larger than that for a standard diamond-metal composite tool.

Voronov, O. A.↗

Synthesizing Diamond from Liquid Feedstock

A relatively economical method of chemical vapor deposition (CVD) has been developed for synthesizing diamond crystals and films. Unlike prior CVD methods for synthesizing diamond, this method does not require precisely proportioned flows of compressed gas feedstocks or the use of electrical discharges to decompose the feedstocks to obtain free radicals needed for deposition chemical reactions. Instead, the feedstocks used in this method are mixtures of common organic liquids that can be prepared in advance, and decomposition of feedstock vapors is effected simply by heating. The feedstock used in this method is a solution comprising between 90 and 99 weight percent of methanol and the balance of one or more other oxyhydrocarbons that could include ethanol, isopropanol, and/or acetone. This mixture of compounds is chosen so that dissociation of molecules results in the desired proportions of carbon-containing radicals (principally, CH3) and of OH, H, and O radicals. Undesirably, the CVD temperature and pressure conditions thermodynamically favor the growth of graphite over the growth of diamond. The H radicals are desirable because they help to stabilize the growing surface of diamond by shifting the thermodynamic balance toward favoring the growth of diamond. The OH and O radicals are desirable because they preferentially etch graphite and other non-diamond carbon, thereby helping to ensure the net deposition of pure diamond. The non-methanol compounds are included in the solution because (1) methanol contains equal numbers of C and O atoms; (2) an excess of C over O is needed to obtain net deposition of diamond; and (3) the non-methanol molecules contain multiple carbon atoms for each oxygen atom and thus supply the needed excess carbon A typical apparatus used in this method includes a reservoir containing the feedstock liquid and a partially evacuated stainless-steel reaction chamber. The reservoir is connected to the chamber via tubing and a needle valve or other suitable flow controller. When the liquid enters the low-pressure environment inside the chamber, it evaporates to form a vapor mixture of the same chemical composition. In addition to the inlet for the feedstock liquid, the chamber is fitted with an outlet connected to a vacuum pump (not shown) through a throttle valve (also not shown) that is automatically controlled to keep the pressure at or near the required value throughout the deposition process. Inside the chamber, a spiral filament made of tungsten, tantalum, graphite, or other high-melting-temperature material is electrically heated to a temperature >2,000 C high enough to cause dissociation of vapor molecules into the aforementioned radicals. A deposition substrate typically, a diamond-polished silicon wafer about 2.5 cm square is positioned about 2 cm away from the filament. The exact location of the substrate is chosen so that the substrate becomes heated by the filament to a deposition temperature in the approximate range of 800 to 1,000 C.

Tzeng, Yonhua↗

Direct-bonded diamond membranes for heterogeneous quantum and electronic technologies

Diamond has superlative material properties for a broad range of quantum and electronic technologies. However, heteroepitaxial growth of single crystal diamond remains limited, impeding integration and evolution of diamond-based technologies. Here, we directly bond single-crystal diamond membranes to a wide variety of materials including silicon, fused silica, sapphire, thermal oxide, and lithium niobate. Our bonding process combines customized membrane synthesis, transfer, and dry surface functionalization, allowing for minimal contamination while providing pathways for near unity yield and scalability. We generate bonded crystalline membranes with thickness as low as 10 nm, sub-nm interfacial regions, and nanometer-scale thickness variability over 200 by 200 μm 2 areas. We measure spin coherence times T 2 for nitrogen vacancy centers in 150 nm-thick bonded membranes of up to 623 ± 21 μs, suitable for advanced quantum applications. We demonstrate multiple methods for integrating high quality factor nanophotonic cavities with the diamond heterostructures, highlighting the platform versatility in quantum photonic applications. Furthermore, we show that our ultra-thin diamond membranes are compatible with total internal reflection fluorescence (TIRF) microscopy, which enables interfacing coherent diamond quantum sensors with living cells while rejecting unwanted background luminescence. The processes demonstrated herein provide a full toolkit to synthesize heterogeneous diamond-based hybrid systems for quantum and electronic technologies.

color center↗

Shock compression of diamond single crystals to 120 GPa: Refractive index and nonlinear photoelasticity

The optical response of transparent solids at extreme conditions is important for both fundamental science and many applications. Strong transparent solids are of particular interest for use as optical windows in dynamic compression experiments. Due to diamond’s exceptional strength and optical properties, laser-driven shock experiments and plate impact experiments were carried out to examine the diamond optical response for shock wave compression along two different crystal orientations. Using laser interferometry at 532 nm and 1550 nm wavelengths, optical transparency was observed and refractive indices were determined for [100] diamond at stresses up to 119 GPa and for [111] diamond at stresses up to 87 GPa. From these results, the nonlinear photoelastic response for [100] and [111] diamond was determined, revealing significant dependence on both crystal orientation and laser wavelength. To enable [100] diamond as an interferometry window in dynamic compression experiments, the requisite window corrections were determined for 532 nm and 1550 nm wavelengths. Because of diamond’s excellent x-ray transparency, the present findings will be particularly useful for incorporating [100] diamonds as windows in dynamic compression experiments involving x-ray diffraction or other x-ray diagnostics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Diamond thin film temperature and heat-flux sensors

Diamond film temperature and heat-flux sensors are developed using a technology compatible with silicon integrated circuit processing. The technology involves diamond nucleation, patterning, doping, and metallization. Multi-sensor test chips were designed and fabricated to study the thermistor behavior. The minimum feature size (device width) for 1st and 2nd generation chips are 160 and 5 micron, respectively. The p-type diamond thermistors on the 1st generation test chip show temperature and response time ranges of 80-1270 K and 0.29-25 microseconds, respectively. An array of diamond thermistors, acting as heat flux sensors, was successfully fabricated on an oxidized Si rod with a diameter of 1 cm. Some problems were encountered in the patterning of the Pt/Ti ohmic contacts on the rod, due mainly to the surface roughness of the diamond film. The use of thermistors with a minimum width of 5 micron (to improve the spatial resolution of measurement) resulted in lithographic problems related to surface roughness of diamond films. We improved the mean surface roughness from 124 nm to 30 nm by using an ultra high nucleation density of 10(exp 11)/sq cm. To deposit thermistors with such small dimensions on a curved surface, a new 3-D diamond patterning technique is currently under development. This involves writing a diamond seed pattern directly on the curved surface by a computer-controlled nozzle.

Aslam, M.↗

Application of Chlorine-Assisted Chemical Vapor Deposition of Diamond at Low Temperatures

Low temperature deposition of diamond has been achieved by a chlorine-assisted diamond chemical vapor deposition (CA-CVD) process. This method begins with the thermal dissociation of molecular chlorine into atomic chlorine in a resistively heated graphite furnace at temperatures between 1300 and 1500 deg. C. The atomic chlorine, upon mixing, subsequently reacts with molecular hydrogen and hydrocarbons. The rapid exchange reactions between the atomic chlorine, molecular hydrogen, and hydrocarbons give rise to the atomic hydrogen and carbon precursors required for diamond deposition. Homoepitaxial diamond growth on diamond substrates has been studied over the substrate temperature range of 100-950 C. It was found that the diamond growth rates are approximately 0.2 microns/hr in the temperature range between 102 and 300 C and that the growth rates do not decrease significantly with a decrease in substrate temperature. This is unique because the traditional diamond deposition using H2/CH4 systems usually disappears at substrate temperatures below approx. 500 deg. C. This opens up a possible route to the deposition of diamond on low-melting point materials such as aluminum and its alloys.

Pan, Chenyu↗

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↗

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↗

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↗

Helium isotopic variability within single diamonds from the Orapa kimberlite pipe

The possible relationships between diamond mineralogy and helium isotopes were investigated by measuring the distribution and isotopic composition of He in a suite of well-characterized one-carat diamonds from the Orapa kimberlite, Botswana. The results of crushing in vacuo experiments indicated that most of He was contained in the matrix, rather than in the inclusions of the diamonds. Step-heating of individual diamonds at 2000 C released He of He-3/He-4 ratios that differed by up to a factor of 100 among the two heating steps, revealing large isotopic variations within individual diamonds. It is suggested that this internal isotopic variability is the result of stepwise graphitization: the first heating step initiates graphitization which nucleates around defects in a diamond, and the second step graphitizes the relatively defect-free regions of the diamond. This explanation predicts that the highest He-3/He-4 ratios should be found in most perfect crystals.

Kurz, Mark D.↗

Diamonds in detonation soot

Diamonds 4 to 7 nm in diameter have been identified and partially isolated from soot formed in detonations of carbon-forming composite explosives. The morphology of the soot has been examined by transmission electron microscopy (TEM), and the identity of the diamond has been established by the electron diffraction pattern of the TEM samples and by the X-ray diffraction (XRD) pattern of the isolated solid. Graphite is also present in the form of ribbons of turbostatic structure with a thickness of 2 to 4 nm. A fraction, about 25 percent of the soot by weight, was recovered from the crude soot after oxidation of the graphite with fuming perchloric acid. This fraction showed a distinct XRD pattern of diamond and the diffuse band of amorphous carbon. The IR spectrum of these diamonds closely matches that of diamonds recovered from meteorites (Lewis et al., 1987), perhaps indicating similar surface properties after the oxidation. If these diamonds are produced in the detonation itself or during the initial expansion, they exhibit a phenomenal crystal growth rate (5 nm/0.00001 s equal 1.8 m/hr) in a medium with a very low hydrogen/carbon ratio. Because the diamonds will be carried along with the expanding gases, they will be accelerated to velocities approaching 8 km/s.

Greiner, N. Roy↗

Electron energy loss spectrometry of interstellar diamonds

The results are reported of electron energy loss spectra (EELS) measurements on diamond residues from carbonaceous meteorites designed to elucidate the structure and composition of interstellar diamonds. Dynamic effective medium theory is used to model the dielectric properties of the diamonds and in particular to synthesize the observed spectra as mixtures of diamond and various pi-bonded carbons. The results are shown to be quantitatively consistent with the idea that diamonds and their surfaces are the only contributors to the electron energy loss spectra of the diamond residues and that these peculiar spectra are the result of the exceptionally small grain size and large specific surface area of the interstellar diamonds.

Bernatowicz, Thomas J.↗

Mechanism for diamond nucleation and growth on single crystal copper surfaces implanted with carbon

The nucleation and growth of diamond crystals on single-crystal copper surfaces implanted with carbon ions is studied. Microwave plasma-enhanced chemical-vapor deposition is used for diamond growth. The single-crystal copper substrates were implanted either at room or elevated temperature with carbon ions prior to diamond nucleation. This procedure leads to the formation of a graphite film on the copper surface which greatly enhances diamond crystallite nucleation. A simple lattice model is constructed for diamond growth on graphite as 111 line (diamond) parallel to 0001 line (graphite) and 110 line (diamond) parallel to 1 1 -2 0 (graphite).

Ong, T. P.↗

Degassing mechanisms of noble gases from carbonado diamonds

Diamonds are unique samples for inferring ancient mantle conditions, because of their enormous stability, antiquity and also of mantle origin. However, as temperatures in the mantle where diamonds have existed are very high (greater than 1000 C) and residence time of some diamonds could be more than a few billion years, it is imperative to examine whether or not diamonds have retained their pristine characteristics, especially those of noble gases, under such extreme conditions. As discussed in a review article by Ozima, there are rather large variations in the diffusivity of helium in diamonds obtained in the early determinations. The data are also limited to temperatures higher than 1200 C. In the present study, we conducted more refined diffusion experiments for He using carbonado diamonds, which have large amounts of radiogenic (4)He approximately 10(exp -2) cu cm STP/g. On the basis of the experimentally estimated diffusion coefficients, we will discuss retentivity of He in diamonds in the mantle condition.

Zashu, S.↗

Ion-Implanted Diamond Films and Their Tribological Properties

This paper reports the physical characterization and tribological evaluation of ion-implanted diamond films. Diamond films were produced by microwave plasma, chemical vapor deposition technique. Diamond films with various grain sizes (0.3 and 3 microns) and roughness (9.1 and 92.1 nm r.m.s. respectively) were implanted with C(+) (m/e = 12) at an ion energy of 160 eV and a fluence of 6.72 x 10(exp 17) ions/sq cm. Unidirectional sliding friction experiments were conducted in ultrahigh vacuum (6.6 x 10(exp -7)Pa), dry nitrogen and humid air (40% RH) environments. The effects of C(+) ion bombardment on fine and coarse-grained diamond films are as follows: the surface morphology of the diamond films did not change; the surface roughness increased (16.3 and 135.3 nm r.m.s.); the diamond structures were damaged and formed a thin layer of amorphous non-diamond carbon; the friction coefficients dramatically decreased in the ultrahigh vacuum (0.1 and 0.4); the friction coefficients decreased slightly in the dry nitrogen and humid air environments.

Wu, Richard L. C.↗