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At least 577 records · Page 32

Formation of diamonds in laser-compressed hydrocarbons at planetary interior conditions

The effects of hydrocarbon reactions and diamond precipitation on the internal structure and evolution of icy giant planets such as Neptune and Uranus have been discussed for more than three decades. Inside these celestial bodies, simple hydrocarbons such as methane, which are highly abundant in the atmospheres, are believed to undergo structural transitions that release hydrogen from deeper layers and may lead to compact stratified cores. Indeed, from the surface towards the core, the isentropes of Uranus and Neptune intersect a temperature–pressure regime in which methane first transforms into a mixture of hydrocarbon polymers, whereas, in deeper layers, a phase separation into diamond and hydrogen may be possible. Here in this paper, we show experimental evidence for this phase separation process obtained by in situ X-ray diffraction from polystyrene (C 8 H 8 ) n samples dynamically compressed to conditions around 150 GPa and 5,000 K; these conditions resemble the environment around 10,000 km below the surfaces of Neptune and Uranus. Our findings demonstrate the necessity of high pressures for initiating carbon–hydrogen separation and imply that diamond precipitation may require pressures about ten times as high as previously indicated by static compression experiments. In conclusion, our results will inform mass–radius relationships of carbon-bearing exoplanets, provide constraints for their internal layer structure and improve evolutionary models of Uranus and Neptune, in which carbon–hydrogen separation could influence the convective heat transport.

79 ASTRONOMY AND ASTROPHYSICS↗

Octo-diamond crystal of nanoscale tetrahedra with interchanging chiral motifs

Despite their simplicity, tetrahedra can assemble into diverse high- and low-density structures. Here we report a low-density ‘octo-diamond’ structure formed by nanoscale solid tetrahedra with a 64-tetrahedron unit cell containing 8 cubic-diamond subcells. The formed crystal is achiral, but is composed of chiral bilayers with alternating handedness. The left- and right-handed chirality of the bilayers, combined with the plasmonic nature of the gold tetrahedra, produces chiroptical responses at the crystal surface. We uncover that the hydrophobic substrate facilitates the arrangement of tetrahedra into irregular ring-like patterns, creating a critical, uneven topography to stabilize the observed octo-diamond structure. This study reveals a potent way to affect colloidal crystallization through particle–substrate interactions, expanding the nanoparticle self-assembly toolbox.

36 MATERIALS SCIENCE↗

Preservation of high-pressure volatiles in nanostructured diamond capsules

High pressure induces dramatic changes and novel phenomena in condensed volatiles(1,2) that are usually not preserved after recovery from pressure vessels. In this study we report a process that pressurizes volatiles into nanopores of type 1 glassy carbon precursors, converts glassy carbon into nanocrystalline diamond by heating and synthesizes free-standing nanostructured diamond capsules (NDCs) capable of permanently preserving volatiles at high pressures, even after release back to ambient conditions for various vacuum-based diagnostic probes including electron microscopy. As a demonstration, we perform a comprehensive study of a high-pressure argon sample preserved in NDCs. Synchrotron X-ray diffraction and high-resolution transmission electron microscopy show nanometre-sized argon crystals at around 22.0 gigapascals embedded in nanocrystalline diamond, energy-dispersive X-ray spectroscopy provides quantitative compositional analysis and electron energy-loss spectroscopy details the chemical bonding nature of high-pressure argon. The preserved pressure of the argon sample inside NDCs can be tuned by controlling NDC synthesis pressure. To test the general applicability of the NDC process, we show that high-pressure neon can also be trapped in NDCs and that type 2 glassy carbon can be used as the precursor container material. Additional experiments on other volatiles and carbon allotropes open the possibility of bringing high-pressure explorations on a par with mainstream condensed-matter investigations and applications.

36 MATERIALS SCIENCE↗

Tailoring diamond’s optical properties via direct femtosecond laser nanostructuring

We demonstrate a rapid, accurate, and convenient method for tailoring the optical properties of diamond surfaces by employing laser induced periodic surface structuring (LIPSSs). The characteristics of the fabricated photonic surfaces were adjusted by tuning the laser wavelength, number of impinging pulses, angle of incidence and polarization state. Using Finite Difference Time Domain (FDTD) modeling, the optical transmissivity and bandwidth was calculated for each fabricated LIPSSs morphology. The highest transmission of ~99.5% was obtained in the near-IR for LIPSSs structures with aspect ratios of the order of ~0.65. The present technique enabled us to identify the main laser parameters involved in the machining process, and to control it with a high degree of accuracy in terms of structure periodicity, morphology and aspect ratio. We also demonstrate and study the conditions for fabricating spatially coherent nanostructures over large areas maintaining a high degree of nanostructure repeatability and optical performance. While our experimental demonstrations have been mainly focused on diamond anti-reflection coatings and gratings, the technique can be easily extended to other materials and applications, such as integrated photonic devices, high power diamond optics, or the construction of photonic surfaces with tailored characteristics in general.

36 MATERIALS SCIENCE↗

An approach for the measurement of the bulk temperature of single crystal diamond using an X-ray free electron laser

We present a method to determine the bulk temperature of a single crystal diamond sample at an X-Ray free electron laser using inelastic X-ray scattering. The experiment was performed at the high energy density instrument at the European XFEL GmbH, Germany. The technique, based on inelastic X-ray scattering and the principle of detailed balance, was demonstrated to give accurate temperature measurements, within 8% for both room temperature diamond and heated diamond to 500 K. Here, the temperature was increased in a controlled way using a resistive heater to test theoretical predictions of the scaling of the signal with temperature. The method was tested by validating the energy of the phonon modes with previous measurements made at room temperature using inelastic X-ray scattering and neutron scattering techniques. This technique could be used to determine the bulk temperature in transient systems with a temporal resolution of 50 fs and for which accurate measurements of thermodynamic properties are vital to build accurate equation of state and transport models.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Direct observation of diamond formation in a shock-compressed high explosive

Understanding the formation timescale and structure of carbonaceous reaction products is critical for modeling the high-pressure equation-of-state of organic materials. We use the National Ignition Facility to shock-compress polycrystalline TATB (C 6 H 6 N 6 O 6 ) samples to ~70–130 GPa and ~4000–5500 K, employing in situ nanosecond X-ray diffraction to probe reaction products and velocimetry to measure transmitted compression wave profiles. Our diffraction data is consistent with the formation of diamond over timescales less than ~60 ns. This represents carbon condensation from a molecular explosive on timescales three times faster than previously reported and the earliest observation of diamond produced from reacting TATB. Reactive flow simulations with explicit chemistry reproduce the observed temporal structure within wave profiles to inform the distribution of P-T states. These findings provide direct evidence of ultrafast diamond formation in a reactive system at extreme conditions and provide new constraints for models of shock and detonation chemistry.

Clarke, Samantha M. [Lawrence Livermore National L↗

Visualization of expanding warm dense gold and diamond heated rapidly by laser-generated ion beams

With the development of several novel heating sources, scientists can now heat a small sample isochorically above 10,000 K. Although matter at such an extreme state, known as warm dense matter, is commonly found in astrophysics (e.g., in planetary cores) as well as in high energy density physics experiments, its properties are not well understood and are difficult to predict theoretically. This is because the approximations made to describe condensed matter or high-temperature plasmas are invalid in this intermediate regime. A sufficiently large warm dense matter sample that is uniformly heated would be ideal for these studies, but has been unavailable to date. We have used a beam of quasi-monoenergetic aluminum ions to heat gold and diamond foils uniformly and isochorically. For the first time, we visualized directly the expanding warm dense gold and diamond with an optical streak camera. Furthermore, we present a new technique to determine the initial temperature of these heated samples from the measured expansion speeds of gold and diamond into vacuum. We anticipate the uniformly heated solid density target will allow for direct quantitative measurements of equation-of-state, conductivity, opacity, and stopping power of warm dense matter, benefiting plasma physics, astrophysics, and nuclear physics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Localized electronic and vibrational states in amorphous diamond

Amorphous diamond structures are generated by quenching high-density high-temperature liquid carbon using tight-binding molecular-dynamics simulations. We show that the generated amorphous diamond structures are predominated by strong tetrahedral bonds with the sp 3 bonding fraction as high as 97%, thus exhibit an ultra-high incompressibility and a wide band gap close to those of crystalline diamond. A small amount of sp 2 bonding defects in the amorphous sample contributes to localized electronic states in the band gap while large local strain gives rise to localization of vibrational modes at both high and low frequency regimes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Explorations of the nonheme high-valent iron-oxo landscape: crystal structure of a synthetic complex with an [Fe IV 2 (μ-O) 2 ] diamond core relevant to the chemistry of sMMOH

Methanotrophic bacteria utilize methane monooxygenase (MMO) to carry out the first step in metabolizing methane. The soluble enzymes employ a hydroxylase component (sMMOH) with a nonheme diiron active site that activates O 2 and generates a powerful oxidant capable of converting methane to methanol. It is proposed that the diiron(II) center in the reduced enzyme reacts with O 2 to generate a diferric-peroxo intermediate called P that then undergoes O–O cleavage to convert into a diiron(IV) derivative called Q, which carries out methane hydroxylation. Most (but not all) of the spectroscopic data of Q accumulated by various groups to date favor the presence of an Fe IV 2 (μ-O) 2 unit with a diamond core. The Que lab has had a long-term interest in making synthetic analogs of iron enzyme intermediates. To this end, the first crystal structure of a complex with a Fe III Fe IV (μ-O) 2 diamond core was reported in 1999, which exhibited an Fe∙∙∙Fe distance of 2.683(1) Å. Now more than 20 years later, a complex with an Fe IV 2 (μ-O) 2 diamond core has been synthesized in sufficient purity to allow diffraction-quality crystals to be grown. Finally, its crystal structure has been solved, revealing an Fe∙∙∙Fe distance of 2.711(4) Å for comparison with structural data for related complexes with lower iron oxidation states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of high energy Au-ion irradiation on the microstructure of diamond films

The effects of 2.245 GeV Au-ion irradiation and subsequent annealing processes on the evolution of microstructure of diamond films with microcrystalline (MCD) or ultra-nanocrystalline (UNCD) granular structure were investigated, using near edge x-ray absorption fine structure and electron energy loss spectroscopy in transmission electron microscopy. For MCD films, the Au-ion irradiation disintegrated some of the diamond grains, resulting in the formation of nano-sized carbon clusters embedded in a matrix of amorphous carbon (a-C). The annealing process recrystallized the diamond grains and converted the a-C into nano-sized graphite particulates and, at the same time, induced the formation of nano-sized i-carbon clusters, the bcc structured carbon with a{sub 0} = 0.432 nm. In contrast, for UNCD films, the Au-ion irradiation transformed the grain boundary phase into nano-sized graphite, but insignificantly altered the crystallinity of the grains of the UNCD films. The annealing process recrystallized the materials. In some of the regions, the residual a-C phases were transformed into nano-sized graphites, whereas in other regions i-carbon nanoclusters were formed. The difference in irradiation-induced microstructural transformation behavior between the MCD and the UNCD films is ascribed to the different granular structures of the two types of films.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Research Update: Direct conversion of amorphous carbon into diamond at ambient pressures and temperatures in air

We report on fundamental discovery of conversion of amorphous carbon into diamond by irradiating amorphous carbon films with nanosecond lasers at room-temperature in air at atmospheric pressure. We can create diamond in the form of nanodiamond (size range <100 nm) and microdiamond (>100 nm). Nanosecond laser pulses are used to melt amorphous diamondlike carbon and create a highly undercooled state, from which various forms of diamond can be formed upon cooling. The quenching from the super undercooled state results in nucleation of nanodiamond. It is found that microdiamonds grow out of highly undercooled state of carbon, with nanodiamond acting as seed crystals.

36 MATERIALS SCIENCE↗

Curved diamond-crystal spectrographs for x-ray free-electron laser noninvasive diagnostics

Here, we report on the manufacturing and X-ray tests of bent diamond-crystal X-ray spectrographs, designed for noninvasive diagnostics of the X-ray free-electron laser (XFEL) spectra in the spectral range from 5 to 15 keV. The key component is a curved, 20-µm thin, single crystalline diamond triangular plate in the (110) orientation. The radius of curvature can be varied between R = 0.6 m and R = 0.1 m in a controlled fashion, ensuring imaging in a spectral window of up to 60 eV for ' 8 keV X-rays. All of the components of the bending mechanism (about 10 parts) are manufactured from diamond, thus ensuring safe operations in intense XFEL beams. The spectrograph is transparent to 88% for 5-keV photons, and to 98% for 15-keV photons. Therefore, it can be used for noninvasive diagnostics of the X-ray spectra during XFEL operations.

47 OTHER INSTRUMENTATION↗

Analysis of the reverse I-V characteristics of diamond-based PIN diodes

Diamond is one of the most promising candidates for high power and high temperature applications, due to its large bandgap and high thermal conductivity. As a result of the growth and fabrication process of diamond-based devices, structural defects such as threading dislocations (TDs) may degrade the electrical properties of such devices. Understanding and control of such defects are important for improving device technology, particularly the reverse breakdown characteristics. Here, we show that the reverse bias current-voltage characteristics in diamond PIN diodes can be described by hopping conduction and Poole-Frenkel emission through TDs over the temperature (T) range of 323 K < T < 423 K, for typical values of the TD density found in epitaxially grown materials.

Saremi, Mehdi (ORCID:0000000150415886)↗

Micro-architecture embedding ultra-thin interlayer to bond diamond and silicon via direct fusion

The continuous demand on miniaturized electronic circuits bearing high power density illuminates the need to modify the silicon-on-insulator-based chip architecture. This is due to the low thermal conductivity of the few hundred nanometer-thick insulator present between the silicon substrate and active layers. The thick insulator is notorious for releasing the heat generated from the active layers during the operation of devices, leading to degradation in their performance and thus reducing their lifetime. To avoid the heat accumulation, we propose a method to fabricate the silicon-on-diamond (SOD) microstructure featured by an exceptionally thin silicon oxycarbide interlayer (~3 nm). While exploiting the diamond as an insulator, we employ spark plasma sintering to render the silicon directly fused to the diamond. Importantly, this process can manufacture the SOD microarchitecture via a simple/rapid way and incorporates the ultra-thin interlayer for minute thermal resistance. The approach invented herein expects to minimize the thermal interfacial resistance of the devices and is thus deemed as a breakthrough appealing to the current chip industry.

36 MATERIALS SCIENCE↗

Graphite to diamond transformation under shock compression: Role of orientational order

To gain insight into the role of orientational order on the shock-induced graphite to diamond phase transformation, three pyrolytic graphite types having different orientational orders were shock-compressed along the average c -axis to peak stresses between 35 and 69 GPa. The materials studied were ZYB-grade highly oriented pyrolytic graphite (HOPG), ZYH-grade HOPG, and as-deposited pyrolytic graphite (PG) having mosaic spreads of 0.8° ± 0.2°, 3.5° ± 1.5°, and ~45°, respectively. Wave profiles, obtained using laser interferometry, show a multiple-wave structure with a distinct, rapid (<10 ns) rise to the high-pressure phase for each graphite type. Multiple-wave profiles, first observed in this study for the less ordered ZYH-grade HOPG and PG samples, show that somewhat poorly oriented pyrolytic graphites also undergo a well-defined phase transformation. Previously, rapid transformation was reported for ZYB-grade but not ZYH-grade HOPG. The measured wave profiles for both HOPG grades are very similar and both grades show a ~22 GPa transformation stress. In contrast, the PG wave profiles are quite different and show a ~46 GPa transformation stress. The continuum results (stress-density states) presented here cannot distinguish between the different high-pressure phases [hexagonal diamond (HD) or cubic diamond] reported in recent x-ray studies. Because ZYB-grade HOPG was recently shown to transform to HD and due to the similar peak states for both HOPG grades, it seems likely that ZYH-grade also transforms into HD. In conclusion, the very different shock responses of PG and HOPG suggest different transformation mechanisms for PG and HOPG, but the high-pressure PG phase remains unclear in the present work.

58 GEOSCIENCES↗

How carbon vacancies can affect the properties of group IV color centers in diamond: A study of thermodynamics and kinetics

Recently, there has been much interest in using Group IV elements from the periodic table to fabricate and study XV color centers in diamond, where X=Si, Ge, Sn, or Pb and V is a carbon vacancy. These Group IV color centers have a number of interesting spin and optical properties, which could potentially make them better candidates than NV− centers for important applications in quantum computing and quantum information processing. Unfortunately, the very same ion implantation process that is required to create these XV color centers in diamond necessarily also produces many carbon vacancies (VC), which can form complexes with these color centers (VC−XV) that can dramatically affect the properties of the isolated XV color centers. The main focus of this work is to use density-functional theory to study the thermodynamics and kinetics of the formation of these VC−XV complexes and to suggest experimental ways to impede this process such as varying the Fermi level of the host diamond material through chemical doping or applying an external electrical bias. We also include a discussion of how the simple presence of many VC can negatively impact the spin coherence times (T2) of Group IV color centers through the presence of acoustic phonons.

Kuate Defo, Rodrick↗

Large microwave inductance of granular boron-doped diamond superconducting films

Boron-doped diamond granular thin films are known to exhibit superconductivity with an optimal critical temperature of T c =7.2 K. Here, we report the measured in-plane complex surface impedance of boron-doped diamond films in the microwave frequency range using a resonant technique. Experimentally measured inductance values are in good agreement with estimates obtained from the normal state sheet resistance of the material. Additionally, the magnetic penetration depth temperature dependence is consistent with that of a fully gapped s-wave superconductor. Boron-doped diamond films should find application where high kinetic inductance is needed, such as microwave kinetic inductance detectors and quantum impedance devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Quantum networks based on color centers in diamond

With the ability to transfer and process quantum information, large-scale quantum networks will enable a suite of fundamentally new applications, from quantum communications to distributed sensing, metrology, and computing. This Perspective reviews requirements for quantum network nodes and color centers in diamond as suitable node candidates. We give a brief overview of state-of-the-art quantum network experiments employing color centers in diamond and discuss future research directions, focusing, in particular, on the control and coherence of qubits that distribute and store entangled states, and on efficient spin–photon interfaces. We discuss a route toward large-scale integrated devices combining color centers in diamond with other photonic materials and give an outlook toward realistic future quantum network protocol implementations and applications.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗