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The phase transitions and equation of state measurements were carried out on rare earth metal Holmium (Ho) to 282 GPa using toroidal diamond anvils thereby doubling the pressure range to which it h...

Density functional theory predictions have been combined with the microwave-plasma chemical vapor deposition technique to explore metastable synthesis of boron-rich boron-carbide materials. A thin film synthesis of high-hardness (up to 37 GPa) B50C2 via chemical vapor deposition was achieved. Characterization of the experimental crystal structure matches well with a new theoretical model structure, with carbon atoms inserted into the boron icosahedra and 2b sites in a α-tetragonal B52 base structure. Previously reported metallic B50C2 structures with carbons inserted only into the 2b or 4c sites are found to be dynamically unstable. The newly predicted structure is insulating and dynamically stable, with a computed hardness value and electrical properties in excellent agreement with the experiment. The present study thus validates the density functional theory calculations of stable crystal structures in boron-rich boron-carbide system and provides a pathway for large-area synthesis of novel materials by the chemical vapor deposition method.

Dysprosium (Dy) has been studied using neutron diffraction under high pressures and low temperatures at a spallation neutron source by employing a large-volume diamond anvil cell. Companion measurements at different central wavelengths allow the collection over extended reciprocal space with momentum transfer Q covering the range from 0.5 A-1 to 5.5 A-1. Upon cooling to 15 K, magnetic ordering was observed in the hexagonal close-packed (hcp), alpha-samarium (α-Sm), and double hexagonal close packed (dhcp) phases of Dy to 22 GPa. We report on previously undetected magnetic superlattice reflections signaling antiferromagnetic transition for both the α-Sm and dhcp phases of Dy. Magnetic structure refinements for the α-Sm phase shows a complex phase comprising two magnetic propagation vectors k = (1/2, 1/2, 1/2) and k = (1/2, 0, 0). Magnetic structure refinements for the dhcp phase yield a single magnetic propagation vector k = (1/2, 0, 1/3) and a possible magnetic space group Pbnma. The refined magnetic structures are provided to the highest pressure of 22 GPa.

Cerium-12at%Praseodymium(Ce0.88Pr0.12) and Ce-50at%Praseodymium(Ce0.50Pr0.50) alloy samples that contain a random solid-solution of Ce (4f1 (J = 5/2)) and Pr (4f2 (J = 4)) localized f-states have b...

The compression behavior of osmium metal was investigated up to 280 GPa (volume compression V/Vo = 0.725) under nonhydrostatic conditions at ambient temperature using angle dispersive axial x-ray diffraction (A-XRD) with a diamond anvil cell (DAC). In addition, shear strength of osmium was measured to 170 GPa using radial x-ray diffraction (R-XRD) technique in DAC. Both diffraction techniques in DAC employed platinum as an internal pressure standard. Density functional theory (DFT) calculations were also performed, and the computed lattice parameters and volumes under compression are in good agreement with the experiments. DFT predicts a monotonous increase in axial ratio (c/a) with pressure and the structural anomalies of less than 1% in (c/a) ratio reported below 150 GPa were not reproduced in theoretical calculations and hydrostatic measurements. The measured value of shear strength of osmium ( τ ) approaches a limiting value of 6 GPa above a pressure of 50 GPa in contrast to theoretical predictions of 24 GPa and is likely due to imperfections in polycrystalline samples. DFT calculations also enable the studies of shear and tensile deformations. The theoretical ideal shear stress is found along the (001)[1–10] shear direction with the maximal shear stress ∼24 GPa at critical strain ∼0.13.

Boron-rich B-C compounds with high hardness have been recently synthesized by the chemical vapor deposition (CVD) method. In this paper, we present our successful efforts in the selective growth of microstructures of boron-carbon compounds on silicon substrates. This was achieved by combining microfabrication techniques such as maskless lithography and sputter deposition with the CVD technique. Our characterization studies on these B-C microstructures showed that they maintain structural and mechanical properties similar to that of their thin-film counterparts. The methodology presented here paves the way for the development of microstructures for microelectromechanical system (MEMS) applications which require custom hardness and strength properties. These hard B-C microstructures are an excellent choice as support structures in MEMS-based devices.

The bulk modulus of nanocrystalline, fluorite-structured samarium doped ceria, Sm0.2Ce0.8O1.9, has been investigated using synchrotron-based high-pressure X-ray diffraction technique. Experiments were carried out under both quasi-hydrostatic condition with silicon oil pressure transmitting medium (PTM) and nonhydrostatic conditions without PTM. The high pressure structural results indicate that the highly defected ionic conductor is stable up to 20 GPa and has a lower bulk modulus than what has been reported for undoped-CeO2. The isothermal bulk modulus of Sm0.2Ce0.8O1.9 is ~ 150–190 GPa compared to ~ 210–220 GPa for CeO2. The collected data experimentally verifies the effect of Sm3 + dopant and oxygen vacancy defect formation on bulk modulus in doped CeO2. The effect of modulus on misfit dislocation formation and dopant ion segregation is discussed in relation to a fundamental understanding of the strain effect in this important family of fast ionic conductors, with potential application as oxygen vacancy conducting solid state electrolytes.

The magnetic ordering in rare earth metals is well established for ambient pressure crystal structures, however, little is known about the magnetic ordering in their corresponding high-pressure crystalline modifications. Holmium (Ho) was studied in a large-volume diamond anvil cell at the Spallation Neutron Source to high-pressure up to 20 GPa and to low-temperature to 10 K. We have conducted two independent high-pressure low-temperature experiments under non-hydrostatic and quasi-hydrostatic pressure conditions respectively. The ambient pressure hexagonal close packed (hcp) phase of holmium shows two magnetic transitions below 10 GPa one to an incommensurate Antiferromagnetic (AFM) phase and another to a conical-Ferromagnetic (c-FM) phase. In contrast, alpha-Samarium-type (α-Sm) phase above 10 GPa and the double hexagonal close packed (dhcp) phase above 19 GPa show only one FM transition marked by the appearance of a magnetic peak at 3 A and the concurrent enhancement of nuclear peaks below 30 K. These new transitions observed by neutron diffraction can be accounted by a commensurate superlattice formation along c-axis in both the α-Sm-type phase and the dhcp phase.

Zirconium (Zr) has properties conducive to nuclear applications and exhibits complex behavior at high pressure with respect to the effects of impurities, deviatoric stress, kinetics, and grain growth which makes it scientifically interesting. Here, we present experimental results on the 300 K equation of state of ultra-high purity Zr obtained using the diamond-anvil cell coupled with synchrotron-based x-ray diffraction and electrical resistance measurements. Based on quasi-hydrostatic room-temperature compression in helium to pressure P = 69.4(2) GPa, we constrain the bulk modulus and its pressure derivative of body-centered cubic (bcc) β-Zr to be K = 224(2) GPa and K′ = 2.6(1) at P = 37.0(1) GPa. A Monte Carlo approach was developed to accurately quantify the uncertainties in K and K′. In the Monte Carlo simulations, both the unit-cell volume and pressure vary according to their experimental uncertainty. Our high-pressure studies do not indicate additional isostructural volume collapse in the bcc phase of Zr in the 56–58 GPa pressure range.

Early stage nucleation morphologies of spatially localized nanocrystalline diamond (NCD) micro-anvils grown on (100)-oriented single crystal diamond (SCD) anvil surfaces were analyzed and investigated for applications in high pressure studies on materials. NCD was grown on SCD using Microwave Plasma Chemical Vapor Deposition (MPCVD) for brief time intervals ranging from 1–15 minutes. Early stage film morphologies were characterized using scanning electron microscopy (SEM) and Raman spectroscopy and were compared to films grown for several hours. Rapid nucleation and growth of NCD on SCD is demonstrated without any pre-growth seeding of the substrate surface. As grown NCD diamond micro-anvils on SCD were used to generate static pressure of 0.5 Terapascal (TPa) on a tungsten sample as measured by synchrotron x-ray diffraction in a diamond anvil cell. Atomic force microscopy (AFM) analysis after decompression from ultrahigh pressures showed that the detachment of the NCD stage occurred in the bulk of the SCD and not at the interface, suggesting significant adhesive bond strength between nanocrystalline and single crystal diamond.

Ultra-high static pressures have been achieved in the laboratory using a two-stage micro-ball nanodiamond anvils as well as a two-stage micro-paired diamond anvils machined using a focused ion-beam system. The two-stage diamond anvils’ designs implemented thus far suffer from a limitation of one diamond anvil sliding past another anvil at extreme conditions. We describe a new method of fabricating two-stage diamond micro-anvils using a tungsten mask on a standard diamond anvil followed by microwave plasma chemical vapor deposition (CVD) homoepitaxial diamond growth. A prototype two-stage diamond anvil with 300 µm culet and with a CVD diamond second stage of 50 µm in diameter was fabricated. We have carried out preliminary high pressure X-ray diffraction studies on a sample of rare-earth metal lutetium sample with a copper pressure standard to 86 GPa. The micro-anvil grown by CVD remained intact during indentation of gasket as well as on decompression from the highest pressure of 86 GPa.

Using a membrane-driven diamond anvil cell and both ac magnetic susceptibility and electrical resistivity measurements, we have characterized the superconducting phase diagram of elemental barium to pressures as high as 65 GPa. We have determined the superconducting properties of the recently discovered Ba-VI crystal structure, which can only be accessed via the application of pressure at low temperature. We find that Ba-VI exhibits a maximum Tc near 8 K, which is substantially higher than the maximum Tc found when pressure is applied at room temperature., 6 pages, 1 table, 3 figures

The most incompressible transition metal osmium (Os) has been studied under high pressure. There is significant interest in Os because of the structural anomalies attributed to topological transitions in the Fermi surface for valence electrons in the hexagonal close-packed phase. We report on measurements of structural parameters and equation of state on Os metal to a pressure of 207 GPa at ambient temperature using platinum as a pressure standard. We obtained angle-dispersive X-ray diffraction data at a synchrotron source with closely spaced pressure intervals to observe any discontinuities or anomalies in the axial c/a ratio at high pressures. Rietveld refinements of X-ray diffraction data show a slowly varying axial ratio (c/a) with a broad minimum at 75 GPa. Our data do not provide any evidence of anomalous behavior in the c/a ratio in Os at 25 or 150 GPa as have been reported in previous studies. Our experimental results are in agreement with theoretical calculations that do not predict any anomalous behavior in c/a ratio in Os under extreme conditions. We present an equation of state for Os to 207 GPa (V/V0 = 0.761) at ambient temperature and compare our results with the previously published data.

High pressure structural transition studies have been carried out on rare earth metal gadolinium in a diamond anvil cell at room temperature to 169 GPa. Gadolinium has been compressed to 38% of its initial volume at this pressure. With increasing pressure, a crystal structure sequence of hcp → Sm-type → dhcp → fcc → dfcc → monoclinic has been observed in our studies on gadolinium. The measured equation of state of gadolinium is presented to 169 GPa at ambient temperature. Magnetic ordering temperature of gadolinium has been studied using designer diamond anvils to a pressure of 25 GPa and a temperature of 10 K. The magnetic ordering temperature has been determined from the four-point electrical resistivity measurements carried out on gadolinium. Our experiments show that the magnetic transition temperature decreases with increasing pressure to 19 GPa and then increases when gadolinium is subjected to higher pressures.

Magnetic ordering temperatures in heavy rare earth metal dysprosium (Dy) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to a pressure of 69 GPa and a temperature of 10 K. Previous studies using magnetic susceptibility measurements at high pressures were able to track magnetic ordering temperature only till 7 GPa in the hexagonal close packed (hcp) phase of Dy. Our studies indicate that the magnetic ordering temperature shows an abrupt drop of 80 K at the hcp-Sm phase transition followed by a gradual decrease that continues till 17 GPa. This is followed by a rapid increase in the magnetic ordering temperatures in the double hcp phase and finally leveling off in the distorted face centered cubic phase of Dy. Our studies reaffirm that 4f-shell remains localized in Dy and there is no loss of magnetic moment or 4f-shell delocalization for pressures up to 69 GPa.

Nanostructured diamond (NSD) films were grown on silicon and Ti–6Al–4V alloy substrates by microwave plasma chemical vapor deposition (MPCVD). NSD Growth rates of 5 µm/h on silicon, and 4 µm/h on Ti–6Al–4V were achieved. In a chemistry of H2/CH4/N2, varying ratios of CH4/H2 and N2/CH4 were employed in this research and their effect on the resulting diamond films were studied by X-ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, and atomic force microscopy. As a result of modifying the stock cooling stage of CVD system, we were able to utilize plasma with high power densities in our NSD growth experiments, enabling us to achieve high growth rates. Substrate temperature and N2/CH4 ratio have been found to be key factors in determining the diamond film quality. NSD films grown as part of this study were shown to contain 85% to 90% sp3 bonded carbon.

Neutron diffraction and electrical transport measurements have been carried out on the heavy rare-earth metal terbium at high pressures and low temperatures in order to elucidate the onset of ferromagnetic (FM) order as a function of pressure. The electrical resistance measurements show a change in slope as the temperature is lowered through the FM Curie temperature. The temperature of this FM transition decreases at a rate of−16.7 K/GPa up to a pressure of 3.6 GPa, at which point the onset of FM order is suppressed. The neutron diffraction measurements as a function of pressure at temperatures ranging from 90 to 290 K confirm that the change of slope in the resistance is associated with the FM ordering, since this occurs at pressures similar to those determined from the resistance results at these temperatures. A disappearance of FM ordering was observed as the pressure is increased above 3.6 GPa and is correlated with the phase transition from the ambient hexagonal close packed structure to an α-Sm-type...

We describe a method for precisely etching small cavities into the culets of diamond anvils for the purpose of providing thermal insulation for samples in experiments at high pressures and high temperatures. The cavities were fabricated using highly directional oxygen plasma to reactively etch into the diamond surface. The lateral extent of the etch was precisely controlled to micron accuracy by etching the diamond through a lithographically fabricated tungsten mask. The performance of the etched cavities in high-temperature experiments in which the samples were either laser heated or electrically heated is discussed.

Superhard boron-carbon materials are of prime interest due to their non-oxidizing properties at high temperatures compared to diamond-based materials and their non-reactivity with ferrous metals under extreme conditions. In this work, evolutionary algorithms combined with density functional theory have been utilized to predict stable structures and properties for the boron-carbon system, including the elusive superhard BC5 compound. We report on the microwave plasma chemical vapor deposition on a silicon substrate of a series of composite materials containing amorphous boron-doped graphitic carbon, boron-doped diamond, and a cubic hard-phase with a boron-content as high as 7.7 at%. The nanoindentation hardness of these composite materials can be tailored from 8 GPa to as high as 62 GPa depending on the growth conditions. These materials have been characterized by electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, X-ray diffraction, and nanoindentation hardness, and the experimental results are compared with theoretical predictions. Our studies show that a significant amount of boron up to 7.7 at% can be accommodated in the cubic phase of diamond and its phonon modes and mechanical properties can be accurately modeled by theory. This cubic hard-phase can be incorporated into amorphous boron-carbon matrices to yield superhard materials with tunable hardness values.

We report our observations on the homoepitaxial diamond growth by microwave plasma chemical vapor deposition (MPCVD) experiments on Type Ib diamond substrates conducted by varying three independent variables. In a feed gas mixture of H2, N2, O2, and 13CH4, the amount of nitrogen was varied in the range of 0 to 4000 ppm, the amount of methane was varied from 2% CH4/H2 to 6% CH4/H2, and the substrate temperature was varied in the range of 850 to 1200 °C. We used isotopically enriched carbon-13 methane gas as the source of carbon in the plasma to clearly distinguish the grown diamond layer from the underlying substrate using Raman spectroscopy. The x-ray rocking curve measurements confirmed the homoepitaxial nature of the deposited layers with a slight increase in the full width at half-maximum for sample grown with the highest nitrogen content in the plasma. Optical and atomic force microscopy revealed dramatic changes in surface morphology with variation in each parameter. The nitrogen incorporation in carbon-13 diamond layers was monitored through photoluminescence spectroscopy of nitrogen–vacancy complexes. A twentyfold increase in diamond growth rate was clearly achieved in this multivariable study.

Gas phase thermodynamic equilibrium calculations involving N2/B2H6/CH4/H2 mixtures were performed to investigate the chemical interactions leading to boron incorporation and microstructure variations in microwave plasma assisted chemical vapor deposition of diamond films. Molecular fractions of several BHx (x = 1–3) species were calculated to study the incorporation mechanism of boron atom into diamond structure. A strong influence of the BH in causing the boron incorporation level in diamond lattice is confirmed by the correlation of its modeled equilibrium composition in the gas phase with boron content as determined experimentally. Nitrogen addition leads to nanocrystallinity and a reduction in boron incorporation due to a decrease in BH as additional B/N/H radicals are formed in the gas phase. We also obtained a good degree of agreement between the theoretically predicted CH3/CN gas phase ratio and the experimental surface roughness trends as measured for all samples.

We report our observations on the catalytic effect of nitrogen in the growth of diamond on top of a diamond anvil substrate by microwave plasma chemical vapor deposition technique. The diamond deposition experiments were carried out by varying the nitrogen content in the range 0–3500 ppm in a standard hydrogen/methane/oxygen plasma. We employ isotopically enriched C-13 methane gas as the source of carbon in the plasma to clearly distinguish the grown diamond layer from the underlying substrate using Raman spectroscopy. The measured diamond growth rate shows a sharp peak at a nitrogen content of 1000 ppm in our growth experiments carried out at 1212°C and atomic force microscopy reveals a dramatic change in surface morphology. Thermodynamic calculations of the plasma show that this growth enhancement could be the result of a competition between the CN and CH3 radicals in the plasma. Finally, we show an application of this ‘unique chemistry’ by synthesizing several designer diamonds with embedded sensors fo...

Background Some loss of joint prostheses has been attributed to osteolytic phenomena leading to loosening and associated with debris from wear of polyethylene articulating against metal alloys. Reduced polyethylene wear has been reported with ceramics serving as an alternative counterface.

The stresses and strains in a diamond anvil cell device were investigated using a finite-element code NIKE2D for the case of an ultra-hard composite gasket material. The pressure distribution in a diamond-coated rhenium gasket was measured by the energy dispersive diffraction technique to 213 GPa and compared with the finite-element modeling results. We examine various models for the mechanical properties of diamond-coated rhenium gasket as well as for diamond failure for shear stresses exceeding 100 GPa. The elastic and plastic properties of gasket were varied such that a good agreement between the experimentally measured pressure distribution and the computational pressure profiles were obtained. As a result, we obtained the effective Young’s modulus, Poisson’s ratio, yield stress for indented gasket, linear hardening modulus, and hardening parameter value for this layered ultra-hard composite gasket material. Future diamond design strategies for attainment of extreme high pressures using ultra-hard gas...

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. 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.

Pressure-induced structural phase transformations in heavy rare earth holmium have been studied in a diamond anvil cell using energy dispersive X-ray diffraction at a synchrotron source to pressures of 62 GPa at ambient temperature. The complete sequence of hcp→Sm-type→dhcp→fcc→dfcc (hR24) is observed for the first time with transitions at 10, 19, 54, and 58 GPa, respectively. The fcc phase is not observed as a pure phase. Each phase transition is correlated to predicted changes in d-band occupation at high pressure. As with many other rare earths, the regions of stability of the several phases are observed to overlap, and significant hysteresis is observed. The measured volume compression for Ho is V/V 0=0.526 at 62 GPa.

We have investigated anisotropic compression effects observed in uranium metal under high pressures by analyzing data obtained with different X-ray diffraction techniques as well as data on samples obtained with different pressure media. Our analysis shows that the observed anisotropic compression effects are independent of the pressure transmitting medium or the experimental technique employed for studying uranium metal under high pressures. This suggests that the observed anisotropic compression effects are not related to non-hydrostatic stresses in the diamond anvil cell devices. First principle calculations using LMT-Art largely reproduce the experimentally measured axial ratios of the orthorhombic unit cell thereby confirming anisotropic effects in this f-band metal under compression.

Using designer diamond anvils and angle dispersive X-ray diffraction technique at a synchrotron source, we have performed simultaneous electrical and structural studies on neodymium metal to 152 GPa in a diamond anvil cell. Four-probe electrical resistance measurement shows a 38% decrease in the electrical resistivity, associated with the delocalization of the 4f-shell electrons, starting at 100 GPa up to a final pressure of 152 GPa. The continuous decrease in electrical resistivity is consistent with the observation of a gradual phase transition to α-U structure in this pressure range. The (1 1 1) diffraction peak of α-U structure first appears at 100 GPa and increases in intensity with increasing pressure to 152 GPa. This increase in intensity is attributed to an increasing volume fraction of α-U phase and an increase in structural y-parameter from 0.07 at 118 GPa to 0.095 at 152 GPa. In contrast to the abrupt pressure-induced f-electron transition seen in cerium and praseodymium, the continuous evoluti...

A wide variety of materials are currently under consideration for use in biomedical implants. Within the scope of certain implants is the need to withstand extensive wear created by repeated use and pressure on high stress joints. Substantial research is directed toward metal-onmetal technology and cobalt chrome molybdenum (CoCrMo) is a prime candidate given its longevity [1]. Wear-resistant surface coatings for the standard CoCrMo biomedical alloy may be a simple and effective way to extend implant lifetime. In this study, we show that an initial plasma nitriding step for CoCrMo alloy is beneficial for attaining adhesion of a nanostructured diamond coating subsequently grown by microwave plasma chemical vapor deposition (CVD). The initial plasma nitriding step is quickly and easily performed in the CVD reactor and results in the formation of chromium nitride phases (CrN, Cr2N) as well as a phase transformation of cobalt from hexagonal to face centered cubic. We suggest that the success in terms of achieving adhesion of the diamond coating to the CoCrMo alloy involves chromium nitride phases acting as a diffusion barrier to carbon, thus preventing direct reaction of carbon with cobalt and the extensive graphitization that would follow.

Bone marrow-derived human mesenchymal stem cells were seeded in serum-free media onto ion beam-deposited nanostructured metalloceramic (Ti-Cr-N) films and plasma-nitrided titanium disks, which were left uncoated as well as precoated with fetal bovine serum. Precoating the disks with serum appears to stimulate cell spreading on both the titanium nitride and metalloceramic materials for as little as 1 hour incubation time. The implication is that both of these materials can adsorb serum proteins in amounts sufficient to influence cell adhesion and spreading for potentially improved in vivo response of orthopedic and dental implants. The materials in this study may prove to exhibit enhanced biological and mechanical properties when compared to conventional micron-scale implant materials such as titanium or cobalt-chrome alloys.

It is generally observed that the rare earth metals adapt an orthorhombic alpha-uranium (α-U) structure at high pressures following the delocalization of 4f shell under compression. We examine the stability of the α-U structure in praseodymium metal at ultrahigh pressures of 313 GPa (volume compression V/V 0 = 0.343) in a diamond anvil cell at room temperature. X-ray diffraction data show a transformation from the α-U structure to a primitive orthorhombic P212121 phase at 147±5 GPa, which is characterized by the anisotropic compressibility of various crystallographic axes. This anisotropic compressibility leads to an interesting situation when the b-axis and the c-axis of the orthorhombic phase become nearly equal above 260 GPa and the structure can be regarded as a pseudo-tetragonal phase. Our present study shows that the 4f band metal Pr does not adapt a body centred tetragonal phase as predicted by theory, but instead novel crystallographic phases are observed at extreme compressions. The present resul...

High pressure magnetic susceptibility experiments can yield valuable insights into the changes in magnetic behavior and electron correlation properties which can accompany extreme compressions of matter. However, magnetic susceptibility experiments with ultrahigh pressure diamond anvil cells are extremely challenging due to the very small size of the high-pressure sample (≈75 μm diameter) and the difficulty of obtaining good coupling between the sample and the sensing coil. As a result, measurement sensitivity and poor signal-to-background ratios tend to be serious concerns which limit the applicability of these experiments. We present here a new approach to high-pressure ac magnetic susceptibility experiments that involve specially fabricated diamond anvils with diamond encapsulated sensing microcoils which are located just 10–20 μm from the high-pressure sample. We also present some test results taken with a gadolinium sample in order to demonstrate the viability of this high-pressure ac susceptibility ...

The atomic volume of rare earth metal dysprosium (Dy) has been measured up to high pressures of 35 GPa and low temperatures between 200 and 7 K in a diamond anvil cell using angle dispersive X-ray diffraction at a synchrotron source. The hexagonal close-packed (hcp), alpha-Samarium (α-Sm), and double hexagonal close-packed (dhcp) phases are observed to be stable in Dy under high-pressure and low-temperature conditions achieved in our experiments. Dy is known to undergo magnetic ordering below 176 K at ambient pressure with magnetic ordering Néel temperature (TN) that changes rapidly with increasing pressure. Our experimental measurement shows that Dy has near-zero thermal expansion in the magnetically ordered state and normal thermal expansion in the paramagnetic state for all the three known high pressure phases (hcp, α-Sm, and dhcp) to 35 GPa. This near-zero thermal expansion behavior in Dy is observed below the magnetic ordering temperature TN at all pressures up to 35 GPa.

We have designed a portable pressure controller module to tune compression rates and maximum pressures attainable in a standard gas-membrane diamond anvil cell (DAC). During preliminary experiments, performed on zirconium (Zr) metal sample, pressure jumps of up to 80 GPa were systematically obtained in less than 0.2s (resulting in compression rate of few GPa/s up to more than 400 GPa/s). In-situ x-ray diffraction and electrical resistance measurements were performed simultaneously during this rapid pressure increase to provide the first time resolved data on α → ω → β structural evolution in Zr at high pressures. Direct control of compression rates and peak pressures, which can be held for prolonged time, allows for investigation of structural evolution and kinetics of structural phase transitions of materials under previously unexplored compression rate-pressure conditions that bridge traditional static and shock/dynamic experimental platforms.

Single-wall carbon nanotube samples were studied under high pressures to 62 GPa using designer diamond anvils with buried electrical microprobes that allowed for monitoring of the four-probe electrical resistance at elevated pressure. After initial densification, the electrical resistance shows a steady increase from 3 to 42 GPa, followed by a sharp rise above 42 GPa. This sharp rise in electrical resistance at high pressures is attributed to opening of an energy band gap with compression. Nanoindentation hardness measurements on the pressure-treated carbon nanotube samples gave a hardness value of 0.50 +/- 0.03 GPa. This hardness value is approximately 2 orders of magnitude lower than the amorphous carbon phase produced in fullerenes under similar conditions. Therefore, the pressure treatment of single-wall carbon nanotubes to 62 GPa did not produce a superhard carbon phase.

Group IV transition metals titanium, zirconium, and hafnium are expected to transform from an ambient hexagonal close packed (hcp, alpha-phase) to a body centered cubic (bcc, beta-phase) at high pressures. This transition path is usually facilitated by the occurrence of an intermediate hexagonal phase (distorted bcc, omega-phase). The existence of a bcc phase in zirconium and hafnium at high pressures has been known for the past ten years; however, its occurrence in titanium has been theoretically predicted but never observed. We report a novel unexpected transformation in titanium metal from an omega phase to an orthorhombic phase (distorted hcp, gamma-phase) at a pressure of 116+/-4 GPa.

Photoluminescence, optical absorption and electron spin resonance results are reported for diamond films homoepitaxially grown by chemical vapor deposition on 〈100〉-oriented natural IIa diamond. Measured dependencies of the corresponding signals on the growth temperature in the range 950–2100°C suggest that, while most of nitrogen is present in our films as single atoms, a small part (approx. 10 −3 of all nitrogen) could be incorporated as N 2 molecules.

Magnetic ordering temperatures in rare earth metal samarium (Sm) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to high-pressure up to 47 GPa and low-temperature to 10 K. The two magnetic transitions at 106 K and 14 K in the α-Sm phase, attributed to antiferromagnetic ordering on hexagonal and cubic layers respectively, collapse in to one magnetic transition near 10 GPa when Sm assumes a double hexagonal close packed (dhcp) phase. On further increase in pressure above 34 GPa, the magnetic transitions split again as Sm adopts a hexagonal-hP3 structure indicating different magnetic transition temperatures for different crystallographic sites. A model for magnetic ordering for the hexagonal-hP3 phase in samarium has been proposed based on the experimental data. The magnetic transition temperatures closely follow the crystallographic symmetry during α-Sm → dhcp → fcc/dist.fcc → hP3 structure sequence at high-pressures and low-temperatures.

Pressure-induced structural phase transformations in a trivalent rare-earth metal praseodymium (Pr) were studied at room temperature in a diamond anvil cell to 103 GPa by energy dispersive x-ray diffraction using a synchrotron source. Our x-ray diffraction studies document the following crystal structure sequence: $\mathrm{dhc}\stackrel{\ensuremath{\rightarrow}}{p}\mathrm{fc}\stackrel{\ensuremath{\rightarrow}}{c}\mathrm{distorted}\mathrm{}\mathrm{fcc}(hR24\mathrm{type})\ensuremath{\rightarrow}\mathrm{monoclinic}(C2/m)\ensuremath{\rightarrow}\ensuremath{\alpha}\ensuremath{-}$uranium with increasing pressure. We measure a 16.7% volume collapse at the transition to the \ensuremath{\alpha}-uranium phase at 20 GPa. The high-pressure \ensuremath{\alpha}-uranium phase in Pr was found to be stable to the highest pressure of 103 GPa, which corresponds to a volume compression ${V/V}_{0}=0.407.$

The light rare-earth metal, neodymium, has been studied up to 155 GPa in a diamond-anvil cell using energy dispersive x-ray diffraction with a synchrotron source. The pressures were calibrated using copper as an internal x-ray pressure standard. A phase transformation from a monoclinic phase $(C2/m,$ $4\mathrm{a}\mathrm{t}\mathrm{o}\mathrm{m}\mathrm{s}/\mathrm{c}\mathrm{e}\mathrm{l}\mathrm{l})$ to an orthorhombic \ensuremath{\alpha}-U phase $(Cmcm,4\mathrm{a}\mathrm{t}\mathrm{o}\mathrm{m}\mathrm{s}/\mathrm{c}\mathrm{e}\mathrm{l}\mathrm{l})$ was observed at 113\ifmmode\pm\else\textpm\fi{}6 GPa without any observable volume collapse. The observation of \ensuremath{\alpha}-U phase in Nd and, previously, in cerium and praseodymium clearly establishes this phase in light rare-earth metals. Our equation of state measurements suggest that delocalization of the f shell in Nd occurs without any volume collapse unlike Ce and Pr.

Diamond anvil cells are used to generate high static pressures up to several megabars (hundreds of GPa) in very small volumes of material. We have explored a technique which employs a microwave plasma chemical vapour deposited diamond layer on one side of the rhenium gasket. The high yield strength of the diamond layer prevents excessive thickness reduction of the sample in the gasket hole. As a test case, we show energy dispersive x-ray diffraction data on rare earth metal neodymium to high pressures of 153 GPa using a synchrotron source. The increased sample thickness results in an unambiguous crystal structure determination of a monoclinic phase in neodymium above 75 GPa.

Ytterbium (Yb), a member of the rare earth group metals with a filled $f$ shell and a divalent electronic character, has been studied under static high pressures in a diamond anvil cell to 202 GPa. We report a new transformation from a face-centered-cubic structure to a hexagonal phase with 3 atoms/cell (space group ${P3}_{1}21$ referred to as $\mathrm{hP}3$) at $98\ifmmode\pm\else\textpm\fi{}5\mathrm{GPa}$. This $\mathrm{hP}3$ phase is similar to that observed in trivalent neodymium and samarium at pressures near 40 GPa. Our high pressure study thus clearly demonstrates that Yb is no longer an ``irregular'' member of the rare earth metals, and divalent to trivalent electronic transition is completed at megabar pressures.

Surgical implant finishing and sterilization procedures were investigated to determine surface characteristics of unalloyed titanium (Ti). All specimens initially were cleaned with phosphoric acid and divided into five groups for comparisons of different surface treatments (C = cleaned as above, no further treatment; CP = C and passivated in nitric acid; CPS = CP and dry-heat sterilized; CPSS = CPS and resterilized; CS = C and dry-heat sterilized). Auger (AES), X-ray photoelectron (XPS), and Raman spectroscopic methods were used to examine surface compositions. The surface oxides formed by all treatments primarily were TiO2, with some Ti2O3 and possibly TiO. Significant concentrations of carbonaceous substances also were observed. The cleaning procedure alone resulted in residual phosphorus, primarily as phosphate groups along with some hydrogen phosphates. A higher percentage of physisorbed water appeared to be associated with the phosphorus. Passivation (with HNO3) alone removed phosphorus from the surface; specimens sterilized without prior passivation showed the thickest oxide and phosphorus profiles, suggesting that passivation alters the oxide characteristics either directly by altering the oxide structure or indirectly by removing moieties that alter the oxide. Raman spectroscopy showed no crystalline order in the oxide. Carbon, oxygen, phosphorus, and nitrogen presence were found to correlate with previously determined surface energy.

Deposition of high-quality diamond films on technology important substrates such as semiconductor silicon is a difficult problem due to inherent interdiffusion problems between substrates and diamond overlayers. To overcome this difficulty the concept of the buffer layer has been utilized and good quality diamond films have been deposited on Si (100) substrates with different kinds of buffer layers. Aluminum nitride (AlN), titanium nitride (TiN), carbon nitride (CN x ), and tungsten carbide (WC) as buffer layers have been studied for diamond nucleation enhancement. Scratching the silicon substrate surface with a diamond paste has also been investigated for diamond nucleation enhancement on Si (100) substrates. The deposited diamond films have been characterized with Raman spectroscopy, and scanning electronic microscopy (SEM) techniques. This study shows that the use of a buffer layer is very effective in enhancing the nucleation rate of diamond films. Finite-volume based computational fluid dynamics has been used to model flow, transport, gas-phase, and surface chemical reactions.

A (100)-oriented natural type-Ia brilliant-cut diamond anvil with thin zirconium electrical probes sputtered onto the culet was coated with an insulating film of diamond using microwave-plasma-enhanced chemical vapour deposition (MPCVD). The critical issue in this high-pressure study is the quality of the homoepitaxial diamond film and its correlation with the mechanical strength of the diamond film/metallic probe interface. We report the first high-pressure study on a homoepitaxial diamond film and underlying zirconium probes to a pressure of 74 GPa. The metallic probes were observed through a transparent lithium fluoride sample with ruby serving as a pressure sensor. After decompression, Raman spectroscopy revealed that the homoepitaxial film was free from deformation and delamination despite the presence of some -bonded carbon at the Zr/diamond interface and within the bulk of the film itself. The present study demonstrates that the presence of residual defects and graphitic impurities has no significant effect on high-pressure applications of homoepitaxial diamond films. This opens up new areas of research with diamond anvil cell devices including those of ohmic heating and electrical transport measurements at ultra-high pressures.

Boron-doped single crystal diamond films were grown homoepitaxially on synthetic (100) Type Ib diamond substrates using microwave plasma assisted chemical vapor deposition. A modification in surface morphology of the film with increasing boron concentration in the plasma has been observed using atomic force microscopy. Use of nitrogen during boron doping has been found to improve the surface morphology and the growth rate of films but it lowers the electrical conductivity of the film. The Raman spectra indicated a zone center optical phonon mode along with a few additional bands at the lower wavenumber regions. The change in the peak profile of the zone center optical phonon mode and its downshift were observed with the increasing boron content in the film. However, sharpening and upshift of Raman line was observed in the film that was grown in presence of nitrogen along with diborane in process gas.

This chapter focuses on the behavior of lanthanide metals from lanthanum to lutetium under extreme conditions of pressure at ambient temperature. The emphasis is on the x-ray diffraction data obtained in the past decade by combining modern diamond anvil cell techniques with the advanced data acquisition and structural refinement techniques at synchrotron x-ray sources. In most lanthanides, data has been obtained to ultrahigh pressure of 200 GPa and a three-fold volume compression at ambient temperature. The ubiquitous rare earth crystal structure sequence hcp → Sm-type → dhcp → fcc → distorted fcc (dfcc) → post-dfcc has been observed in lanthanides under high pressures. The structural changes up to dfcc phase have been attributed to the regular trivalent behavior and driven by sp →d electron transfer under pressure. Detailed structural refinements have confirmed that a hR24 hexagonal structure with 24 atoms/cell best describes the “ dfcc phase” in lanthanides under high pressures. The post-dfcc phases are generally attributed to the delocalization of 4f-shell under extreme conditions. A variety of crystal structures have been observed for the “ post-dfcc phase” including body-centered tetragonal ( bct ), alpha-Uranium ( α-U ) and monoclinic ( C2/m ) structure along with other low-symmetry crystal structures. The most pervasive is the monoclinic ( C2/m ) structure at ultrahigh pressures with transition pressure increasing from 5 GPa for cerium to 124 GPa for thulium. The measured Pressure-Volume (P-V) relation or equation of state data is also presented for lanthanides under extreme conditions.

The boron-doped single crystal diamond films were grown homoepitaxially on synthetic (100) oriented Type Ib diamond substrates using a Microwave Plasma Chemical Vapor Deposition (MPCVD) technique. Raman spectrum showed a few additional bands at the lower wavenumber regions along with the zone center optical phonon mode for diamond. The change in the peak profile of the zone center optical phonon mode and its downshift were observed with the increasing boron content in the film. A modification in surface morphology of the film with increasing boron content had been observed by atomic force microscopy. Four point probe electrical measurement indicated that different conduction mechanisms are operating in various temperature regions for these semiconducting films.

We report high-pressure and high-temperature studies on a series of oxide garnets of chemical composition ${A}_{3}{B}_{2}{C}_{3}{\mathrm{O}}_{12}$. The members of this family investigated are gadolinium scandium gallium garnet (GSGG), gadolinium gallium garnet (GGG), and yttrium aluminum garnet (YAG). The GSGG and GGG are doped with both neodymium and chromium while the YAG is doped only with neodymium. Photoluminescence, synchrotron x-ray-diffraction, and laser heating studies were carried out in a diamond-anvil cell. Variety of optical sensors (ruby, Sm-doped YAG) and x-ray pressure marker (copper) were employed for pressure measurement. Pressure-induced amorphization was observed in GSGG at 58\ifmmode\pm\else\textpm\fi{}3 GPa and GGG at 84\ifmmode\pm\else\textpm\fi{}4 GPa by x-ray-diffraction studies. The photoluminescence studies show only gradual broadening of emission bands through the amorphization transition. On increasing pressure beyond amorphization, very broad and featureless emission bands were observed in the fluorescence spectra at 77\ifmmode\pm\else\textpm\fi{}2 GPa for GSGG and at 88\ifmmode\pm\else\textpm\fi{}2 GPa for GGG. Laser heating of the pressure-induced amorphous phase in GSGG caused recrystallization to the stable cubic phase. High-pressure x-ray study on YAG shows that it retains cubic phase up to 101\ifmmode\pm\else\textpm\fi{}4 GPa. A pressure-volume relation for each member of the oxide garnet at ambient temperatures is presented, structural transformation mechanisms, and application of oxide garnets as pressure sensors are also discussed.