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O2 is diamond structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. O is bonded to four equivalent O atoms to form corner-sharing OO4 tetrahedra. All O–O bond lengths are 1.86 Å.
TaCl3 is diamond structured and crystallizes in the cubic Fd-3m space group. The structure is zero-dimensional and consists of eight TaCl3 clusters. Ta3+ is bonded to five Cl1- atoms to form corner-sharing TaCl5 square pyramids. There are one shorter (2.40 Å) and four longer (2.44 Å) Ta–Cl bond lengths. There are two inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one Ta3+ atom. In the second Cl1- site, Cl1- is bonded in a distorted L-shaped geometry to two equivalent Ta3+ atoms.
This report presents the results of the secondary electron emission spectroscopy study of hydrogenated diamond surfaces for single crystals and chemical vapor-deposited polycrystalline films. One-electron calculations of Auger spectra of diamond surfaces having various hydrogen coverages are presented, the major features of the experimental spectra are explained, and a theoretical model for Auger spectra of hydrogenated diamond surfaces is proposed. An energy shift and a change in the line shape of the carbon core-valence-valence (KVV) Auger spectra were observed for diamond surfaces after exposure to an electron beam or by annealing at temperatures higher than 950 C. This change is related to the redistribution of the valence-band local density of states caused by hydrogen desorption from the surface. A strong negative electron affinity (NEA) effect, which appeared as a large, narrow peak in the low-energy portion of the spectrum of the secondary electron energy distribution, was also observed on the diamond surfaces. A fine structure in this peak, which was found for the first time, reflected the energy structure of the bottom of the conduction band. Further, the breakup of the bulk excitons at the surface during secondary electron emission was attributed to one of the features of this structure. The study demonstrated that the NEA type depends on the extent of hydrogen coverage of the diamond surface, changing from the true type for the completely hydrogenated surface to the effective type for the partially hydrogenated surface.
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The crystallinity of large HEM silicon ingots as a function of heat flow conditions is investigated. A balanced heat flow at the bottom of the ingot restricts spurious nucleation to the edge of the melted-back seed in contact with the crucible. Homogeneous resistivity distribution over all the ingot has been achieved. The positioning of diamonds electroplated on wirepacks used to slice silicon crystals is considered. The electroplating of diamonds on only the cutting edge is described and the improved slicing performance of these wires evaluated. An economic analysis of value added costs of HEM ingot casting and band saw sectioning indicates the projected add on cost of HEM is well below the 1986 allocation.
We report on the structural verification of metastable ice VII solidifying in the phase space of ice VI at 1.80 GPa at room temperature. Using time-resolved (TR) x-ray diffraction and TR ruby luminescence paired with high-speed microphotography utilizing a dynamic diamond anvil cell, an initial compression rate range from 0.12 to 95.84 GPa/s was explored. The solidification pressure of metastable ice VII has a potential sigmoidal dependence upon compression rate with a turnover compression rate of ∼80 GPa/s. The preferred crystallization of ice VII in the stability field of ice VI is due to the increased nucleation rate of ice VII over ice VI at 1.77 GPa that is driven by the surface energy difference between the liquid and solid phases along with the change in Gibbs free energy of solidification. The dynamic pressure-volume–compression behaviors of ice phases (VI and VII) show a lattice stiffening in both phases, especially during the compression loading. It is also found that the compression rate greatly affects the solid-solid phase transition between ice VI and VII but does not affect the liquid-solid transition between water and ice VI as much. Lastly, a third phase transition was found to occur after metastable ice VII transforms into high-density amorphous (HDA) ice, which could be a disordered hydrogen-bonded network configuration of ice VII forming out of HDA ice facilitated by the decoupling of the oxygen movement and reorientation of the H 2 O molecule. These results demonstrate the complexity of a seemingly simple molecule H 2 O, how it can readily change its static properties with the modification of (de)compression rate, and highlight the need to use multiple TR structural and spectroscopic probes at higher time resolutions to realize the most comprehensive understanding.
In an extension of our previous work, the measurements of temperature dependent magnetization associated with trapped magnetic flux in a small single crystal of CaKFe 4 As 4 , using zero - field - cooled and field - cooled protocols were performed, on the same crystal, at ambient pressure without a pressure cell and at 2.2 GPa in a commercial diamond anvil cell (DAC), showing comparable results. The data show that with a proper care and understanding, trapped flux measurements in superconductors indeed can be performed on samples in DACs under pressure, as was done on superhydrides.
A revolution in the diamond technology is in progress, as the low-pressure process becomes an industrial reality. It will soon be possible to take advantage of the demanding properties of diamond to develop a myriad of new applications, particularly for self-lubricating, wear-resistant, and superhard coatings. The production of large diamond films or sheets at low cost, a distinct possibility in the not-too-distant future, may drastically change tribology technology, particularly regarding solid lubricants and lubricating materials and systems. This paper reviews the structures and properties of natural and synthetic diamonds to gain a better understanding of the tribological properties of diamond and related materials. Atomic and crystal structure, impurities, mechanical properties, and indentation hardness of diamond are described.
Cubic boron nitride (c-BN), with a small 1.4% lattice mismatch with diamond, presents a heterostructure with multiple opportunities for electronic device applications. However, the formation of c-BN/diamond heterostructures has been limited by the tendency to form hexagonal BN at the interface. In this study, c-BN has been deposited on free standing polycrystalline and single crystal boron-doped diamond substrates via electron cyclotron resonance plasma enhanced chemical vapor deposition (ECR-PECVD), employing fluorine chemistry. In situ x-ray photoelectron spectroscopy (XPS) is used to characterize the nucleation and growth of boron nitride (BN) films as a function of hydrogen gas flow rates during deposition. The PECVD growth rate of BN was found to increase with increased hydrogen gas flow. In the absence of hydrogen gas flow, the BN layer was reduced in thickness or etched. The XPS results show that an excess of hydrogen gas significantly increases the percent of sp2 bonding, characteristic of hexagonal BN (h-BN), particularly during initial layer growth. Reducing the hydrogen flow, such that hydrogen gas is the limiting reactant, minimizes the sp2 bonding during the nucleation of BN. TEM results indicate the partial coverage of the diamond with thin epitaxial islands of c-BN. The limited hydrogen reaction is found to be a favorable growth environment for c-BN on boron-doped diamond.
High thermal conductivity electronic materials are critical components for high-performance electronic and photonic devices as both active functional materials and thermal management materials. We report an isotropic high thermal conductivity exceeding 500 W m –1 K –1 at room temperature in high-quality wafer-scale cubic silicon carbide (3C-SiC) crystals, which is the second highest among large crystals (only surpassed by diamond). Furthermore, the corresponding 3C-SiC thin films are found to have record-high in-plane and cross-plane thermal conductivity, even higher than diamond thin films with equivalent thicknesses. Our results resolve a long-standing puzzle that the literature values of thermal conductivity for 3C-SiC are lower than the structurally more complex 6H-SiC. We show that the observed high thermal conductivity in this work arises from the high purity and high crystal quality of 3C-SiC crystals which avoids the exceptionally strong defect-phonon scatterings. Moreover, 3C-SiC is a SiC polytype which can be epitaxially grown on Si. We show that the measured 3C-SiC-Si thermal boundary conductance is among the highest for semiconductor interfaces. These findings provide insights for fundamental phonon transport mechanisms, and suggest that 3C-SiC is an excellent wide-bandgap semiconductor for applications of next-generation power electronics as both active components and substrates.
Much is unknown about how phase transitions link to micro-/nano-structures in high-entropy systems, especially under extreme pressure and temperature conditions. This work studies the evolution of dual-phase nanolamellar eutectic high-entropy alloy phases of AlCoCrFeNi 2.1 generated by laser powder-bed fusion (L-PBF) for pressures up to 42 GPa. We compare quasi-hydrostatic high pressure synchrotron x-ray diffraction studies on L-PBF printed cylindrical samples up to 5.5 GPa (large-volume Paris–Edinburgh cell) to those carried out on an L-PBF printed foil in a diamond anvil cell where the pressure reached 42 GPa. Our results show that the initially alternating face-centered cubic (FCC) and body-centered cubic (BCC) nanolamellar structure of AlCoCrFeNi 2.1 transformed into single-phase FCC nanolamellae under high pressure with BCC–FCC phase transformation completion at 21 ± 3 GPa. Our results indicate a diffusionless BCC–FCC transformation in this additively manufactured far-from-equilibrium microstructure and demonstrate that the FCC phase is stable up to very high pressures. The measured equation of state for the FCC phase of AlCoCrFeNi 2.1 is presented up to 42 GPa and shows excellent agreement between the data obtained in large-volume press and diamond anvil cell experiments.
The negatively charged tin-vacancy center in diamond (SnV − ) is an excellent solid state qubit with optically-addressable transitions and a long electron spin coherence time at elevated (∼1.7 K). However, implementing scalable quantum nodes with high-fidelity optical readout of the electron spin state requires efficient photon emission and collection from the system. Here, in this manuscript, we report a quantum photonic interface for SnV−centers based on one-dimensional photonic crystal cavities fabricated in diamond thin films. Furthermore, we provide a rigorous description of the spontaneous emission dynamics of our system, taking into account individual contributions from both the C and D transitions of the emitter. This allows for determination of Purcell factors per transition and, by extension, the C/D branching ratio SnV− zero phonon line. We observe quality factors up to ~6000 across this sample, and measure up to a 12-fold lifetime reduction, which translates into a Purcell factor of 𝐹 𝐶 =26.2±1.5 for a targeted C transition. By considering the cavity mode polarization alignment with the C and D transition dipole moments, we validate the C/D branching ratio to be 𝜂 BR =0.75±0.01, in line with previous theoretical and experimental findings.
Self-assembly of isotropically interacting particles into desired crystal structures could allow for creating designed functional materials via simple synthetic means. However, the ability to use isotropic particles to assemble different crystal types remains challenging, especially for generating low-coordinated crystal structures. Here, we demonstrate that isotropic pairwise interparticle interactions can be rationally tuned through the design of DNA shells in a range that allows transition from common, high-coordinated FCC-CuAu and BCC-CsCl lattices, to more exotic symmetries for spherical particles such as the SC-NaCl lattice and to low-coordinated crystal structures (i.e., cubic diamond, open honeycomb). The combination of computational and experimental approaches reveals such a design strategy using DNA-functionalized nanoparticles and successfully demonstrates the realization of BCC-CsCl, SC-NaCl, and a weakly ordered cubic diamond phase. The study reveals the phase behavior of isotropic nanoparticles for DNA–shell tunable interaction, which, due to the ease of synthesis is promising for the practical realization of non-close-packed lattices.
Little is known regarding the liquid structure of materials compressed to extreme conditions, and even less is known about liquid structures undergoing rapid compression on nanosecond timescales. Here, we report on liquid structure factor and radial distribution function measurements of tin shock compressed to 84(19) GPa. High-quality, femtosecond x-ray diffraction measurements at the Linac Coherent Light Source were used to extract the liquid diffuse scattering signal. From the radial distribution function, we find that the structural evolution of the liquid with increasing pressure mimics the evolution of the solid phase. With increasing pressure, we find that the liquid structure evolves from a complex structure, with a low coordination number, to a simple liquid structure with a coordination number of ~12. We provide a pathway for future experiments to study liquids at elevated pressures using high-energy lasers to shock compress materials beyond the reach of static diamond anvil cell techniques.
An emerging class of superhard materials for extreme environment applications are compounds formed by heavy transition metals with light elements. In this work, ultrahigh pressure experiments on transition metal rhenium diboride (ReB 2 ) were carried out in a diamond anvil cell under isothermal and non-hydrostatic compression. Two independent high-pressure experiments were carried out on ReB 2 for the first time up to a pressure of 241 GPa (volume compression V/V 0 = 0.731 ± 0.004), with platinum as an internal pressure standard in X-ray diffraction studies. The hexagonal phase of ReB 2 was stable under highest pressure, and the anisotropy between the a-axis and c-axis compression increases with pressure to 241 GPa. The measured equation of state (EOS) above the yield stress of ReB 2 is well represented by the bulk modulus K 0 = 364 GPa and its first pressure derivative K 0 ´ = 3.53. Corresponding density-functional-theory (DFT) simulations of the EOS and elastic constants agreed well with the experimental data. DFT results indicated that ReB 2 becomes more ductile with enhanced tendency towards metallic bonding under compression. The DFT results also showed strong crystal anisotropy up to the maximum pressure under study. The pressure-enhanced electron density distribution along the Re and B bond direction renders the material highly incompressible along the c-axis. Our study helps to establish the fundamental basis for anisotropic compression of ReB 2 under ultrahigh pressures
Nanocrystals can exist in multiply twinned structures like icosahedron or single crystalline structures like cuboctahedron. Transformations between these structures can proceed through diffusion or displacive motion. Experimental studies on nanocrystal structural transformations have focused on high-temperature diffusion-mediated processes. Limited experimental evidence of displacive motion exists. We report structural transformation of 6 nm Au nanocrystals under nonhydrostatic pressure of 7.7 GPa in a diamond anvil cell that is driven by displacive motion. X-ray diffraction and transmission electron microscopy were used to detect the structural transformation from multiply twinned to single crystalline. Single crystalline nanocrystals were recovered after unloading, then quickly reverted to the multiply twinned state after dispersion in toluene. Furthermore, the dynamics of recovery was captured using TEM which showed surface recrystallization and rapid twin boundary motion. Molecular dynamics simulations showed that twin boundaries are unstable due to defects nucleated from the interior of the nanocrystal.
Abstract Transition metal nitrides, particularly those of 5 d metals, are known for their outstanding properties, often relevant for industrial applications. Among these metal elements, tungsten is especially attractive given its low cost. In this high‐pressure investigation of the W–N system, two novel ultra‐incompressible tungsten nitride superconductors, namely W 2 N 3 and W 3 N 5 , are successfully synthesized at 35 and 56 GPa, respectively, through a direct reaction between N 2 and W in laser‐heated diamond anvil cells. Their crystal structure is determined using synchrotron single‐crystal X‐ray diffraction. While the W 2 N 3 solid's sole constituting nitrogen species are N 3‐ units, W 3 N 5 features both discrete N 3‐ as well as N 2 4‐ pernitride anions. The bulk modulus of W 2 N 3 and W 3 N 5 is experimentally determined to be 380(3) and 406(7) GPa, and their ultra‐incompressible behavior is rationalized by their constituting WN 7 polyhedra and their linkages. Importantly, both W 2 N 3 and W 3 N 5 are recoverable to ambient conditions and stable in air. Density functional theory calculations reveal W 2 N 3 and W 3 N 5 to have a Vickers hardness of 30 and 34 GPa, and superconducting transition temperatures at ambient pressure (50 GPa) of 11.6 K (9.8 K) and 9.4 K (7.2 K), respectively. Additionally, transport measurements performed at 50 GPa on W 2 N 3 corroborate with the calculations.