Diamond-based HBAR as a high-pressure sensor.

Features of an application of a High-overtone Bulk Acoustic Resonator (HBAR) as a high-pressure sensor have been considered. In this way, the second version of an integrated measurement system combining a Diamond Anvil Cell (DAC) and an HBAR operating in the microwave frequency band from 1.3 to 3.7 GHz was developed. A specific configuration of HBAR based on a piezoelectric layered structure as "Al/ASN/Mo/(100) diamond" was proposed. Two independent methods of pressure control were used to calibrate the embedded HBAR as a pressure sensor: a stress-induced shift of the diamond Raman line and the shift of the R1 luminescence line of Cr3+ in the ruby matrix. A stable correlation between the frequency shifts of the acoustic overtones in the HBAR, the shift of the diamond Raman line and the shift of the R1 line with a change in pressure applied to the W-gasket with embedded ruby particles was established in the range of 0 … 30 GPa. The sensitivity of an investigated sensor to the pressure variation was found to be equal 1ΔPΔff=4.8∙10-4GPa-1. The maximal value of 30 GPa obtained in a given work can be easily increased after a minor reconfiguration of the DAC. Considering the range of 0 - 5 GPa a proposed built-in DAC acoustoelectronic sensor has the better performance and sensitivity compared with known methods of a pressure measurement.

Structure Investigations of Islands with Atomic-Scale Boron-Carbon Bilayers in Heavily Boron-Doped Diamond Single Crystal: Origin of Stepwise Tensile Stress.

The detailed studies of the surface structure of synthetic boron-doped diamond single crystals using both conventional X-ray and synchrotron nano- and microbeam diffraction, as well as atomic force microscopy and micro-Raman spectroscopy, were carried out to clarify the recently discovered features in them. The arbitrary shaped islands towering above the (111) diamond surface are formed at the final stage of the crystal growth. Their lateral dimensions are from several to tens of microns and their height is from 0.5 to 3 µm. The highly nonequilibrium conditions of crystal growth enhance the boron solubility and, therefore, lead to an increase of the boron concentrations in the islands on the surface up to 1022 cm-3, eventually generating significant stresses in them. The stress in the islands is found to be the volumetric tensile stress. This conclusion is based on the stepwise shift of the diamond Raman peak toward lower frequencies from 1328 to 1300 cm-1 in various islands and on the observation of the shift of three low-intensity reflections at 2-theta Bragg angles of 41.468°, 41.940° and 42.413° in the X-ray diffractogram to the left relative to the (111) diamond reflection at 2theta = 43.93°. We believe that the origin of the stepwise tensile stress is a discrete change in the distances between boron-carbon layers with the step of 6.18 Å. This supposition explains also the stepwise (step of 5 cm-1) behavior of the diamond Raman peak shift. Two approaches based on the combined application of Raman scattering and X-ray diffraction data allowed determination of the values of stresses both in lateral and normal directions. The maximum tensile stress in the direction normal to the surface reaches 63.6 GPa, close to the fracture limit of diamond, equal to 90 GPa along the [111] crystallographic direction. The presented experimental results unambiguously confirm our previously proposed structural model of the boron-doped diamond containing two-dimensional boron-carbon nanosheets and bilayers.

Excitation of hypersonic acoustic waves in diamond-based piezoelectric layered structure on the microwave frequencies up to 20GHz.

First ultrahigh frequency (UHF) investigation of quality factor Q for the piezoelectric layered structure «Al/(001)AlN/Mo/(100) diamond¼ has been executed in a broad frequency band from 1 up to 20GHz. The record-breaking Q·f quality parameter up to 2.7·1014Hz has been obtained close to 20GHz. Frequency dependence of the form factor m correlated with quality factor has been analyzed by means of computer simulation, and non-monotonic frequency dependence can be explained by proper features of thin-film piezoelectric transducer (TFPT). Excluding the minimal Q magnitudes measured at the frequency points associated with minimal TFPT effectiveness, one can prove a rule of Qf∼f observed for diamond on the frequencies above 1GHz and defined by Landau-Rumer's acoustic attenuation mechanism. Synthetic IIa-type diamond single crystal as a substrate material for High-overtone Bulk Acoustic Resonator (HBAR) possesses some excellent acoustic properties in a wide microwave band and can be successfully applied for design of acoustoelectronic devices, especially the ones operating at a far UHF band.

Formation of Boron-Carbon Nanosheets and Bilayers in Boron-Doped Diamond: Origin of Metallicity and Superconductivity.

The insufficient data on a structure of the boron-doped diamond (BDD) has frustrated efforts to fully understand the fascinating electronic properties of this material and how they evolve with doping. We have employed X-ray diffraction and Raman scattering for detailed study of the large-sized BDD single crystals. We demonstrate a formation of boron-carbon (B-C) nanosheets and bilayers in BDD with increasing boron concentration. An incorporation of two boron atoms in the diamond unit cell plays a key role for the B-C nanosheets and bilayer formation. Evidence for these B-C bilayers which are parallel to {111} planes is provided by the observation of high-order, super-lattice reflections in X-ray diffraction and Laue patterns. B-C nanosheets and bilayers minimize the strain energy and affect the electronic structure of BDD. A new shallow acceptor level associated with B-C nanosheets at ~37 meV and the spin-orbit splitting of the valence band of ~6 meV are observed in electronic Raman scattering. We identified that the superconducting transitions occur in the (111) BDD surfaces only. We believe that the origin of Mott and superconducting transitions is associated with the two-dimensional (2D) misfit layer structure of BDD. A model for the BDD crystal structure, based on X-ray and Raman data, is proposed and confirmed by density functional theoretical calculation.

Toward the Ultra-incompressible Carbon Materials. Computational Simulation and Experimental Observation.

The common opinion that diamond is the stiffest material is disproved by a number of experimental studies where the fabrication of carbon materials based on polymerized fullerenes with outstanding mechanical stiffness was reported. Here we investigated the nature of this unusual effect. We present a model constituted of compressed polymerized fullerite clusters implemented in a diamond matrix with bulk modulus B0 much higher than that of diamond. The calculated B0 value depends on the sizes of both fullerite grain and diamond environment and shows close correspondence with measured data. Additionally, we provide results of experimental study of atomic structure and mechanical properties of ultrahard carbon material supported the presented model.

Demonstration of simultaneous experiments using thin crystal multiplexing at the Linac Coherent Light Source.

Multiplexing of the Linac Coherent Light Source beam was demonstrated for hard X-rays by spectral division using a near-perfect diamond thin-crystal monochromator operating in the Bragg geometry. The wavefront and coherence properties of both the reflected and transmitted beams were well preserved, thus allowing simultaneous measurements at two separate instruments. In this report, the structure determination of a prototypical protein was performed using serial femtosecond crystallography simultaneously with a femtosecond time-resolved XANES studies of photoexcited spin transition dynamics in an iron spin-crossover system. The results of both experiments using the multiplexed beams are similar to those obtained separately, using a dedicated beam, with no significant differences in quality.

All-diamond optical assemblies for a beam-multiplexing X-ray monochromator at the Linac Coherent Light Source.

A double-crystal diamond (111) monochromator recently implemented at the Linac Coherent Light Source (LCLS) enables splitting of the primary X-ray beam into a pink (transmitted) and a monochromatic (reflected) branch. The first monochromator crystal, with a thickness of ∼100 µm, provides sufficient X-ray transmittance to enable simultaneous operation of two beamlines. This article reports the design, fabrication and X-ray characterization of the first and second (300 µm-thick) crystals utilized in the monochromator and the optical assemblies holding these crystals. Each crystal plate has a region of about 5 × 2 mm with low defect concentration, sufficient for use in X-ray optics at the LCLS. The optical assemblies holding the crystals were designed to provide mounting on a rigid substrate and to minimize mounting-induced crystal strain. The induced strain was evaluated using double-crystal X-ray topography and was found to be small over the 5 × 2 mm working regions of the crystals.

Hybrid diamond-silicon angular-dispersive x-ray monochromator with 0.25-meV energy bandwidth and high spectral efficiency.

We report on the design, implementation, and performance of an x-ray monochromator with ultra-high energy resolution (ΔE/E ≃ 2.7 × 10(-8)) and high spectral efficiency using x rays with photon energies E ≃ 9.13 keV. The operating principle of the monochromator is based on the phenomenon of angular dispersion in Bragg back-diffraction. The optical scheme of the monochromator is a modification of a scheme reported earlier [Shvyd'ko et al., Phys. Rev. A 84, 053823 (2011)], where a collimator/wavelength selector Si crystal was replaced with a 100-µm-thick type IIa diamond crystal. This modification provides a very-small-energy bandwidth ΔE ≃ 0.25 meV, a 3-fold increase in the aperture of the accepted beam, a reduction in the cumulative angular dispersion rate of x rays emanating from the monochromator for better focusing on a sample, a sufficient angular acceptance matching the angular divergence of an undulator source (≈ 10 µrad), and an improved throughput due to low x-ray absorption in the thin diamond crystal. The measured spectral efficiency of the monochromator was ≈ 65% with an aperture of 0.3 × 1 mm(2). The performance parameters of the monochromator are suitable for inelastic x-ray spectroscopy with an absolute energy resolution ΔE < 1 meV.

Pulse acoustic microscopy characterization of the elastic properties of nanostructured metal-nanocarbon composites (Declercq/ICU'07).

New metal-nanocarbon composites were obtained by high-energy (ball milling) pre-treatment of the powder mixture followed by high-pressure/high-temperature treatment. Acoustic microscopy was used to study elastic properties and bulk irregularities of the samples.

Novel method of flat cold cathode formation from carbon-nitrogen nanofibers.

A novel method of high-efficiency cold cathode formation is developed. The technique is based on the growth of nitrogenated carbon nanofibers in a high-pressure apparatus on a graphite substrate. An average nitrogen concentration up to 13% was achieved. The turn-on and threshold fields for such cathodes are substantially lower than those for cathodes based on other carbon materials. A special method of substrate preparation provides strong adhesion of carbon-nitrogen nanomaterial and its durability during long-term cathode operation. It is shown that due to high uniformity, emission efficiency and time reliability, the field emission cathodes based on carbon-nitrogen nanofibers (CNNs) are very promising for high-brightness flat indicators and displays.

Synthesis of carbon-nitrogen nanostructures by hot isostatic pressure apparatus and their field emission properties.

Carbon-nitrogen (CN) nanofibers were synthesized in argon-nitrogen gas mixture at 75 MPa by high isostatic pressure (HIP) apparatus using a graphite resistive heater. The CN nanofibers were grown in random with the diameter of about 200 nm and the length over 5 microm. The structures obtained can be divided bamboo-like, spring-like, and bead necklace-like CN nanofibers. The nitrogen content of up to 8.4% was found in CN nanofibers by EELS analysis. Field emission results showed that the density of field emitters and the field enhancement factors changed by surface treatments and that CN nanofibers contained glass frit. The screen-printed CN nanofiber had a turn-on field of 2 V/microm.

3D spectrum imaging of multi-wall carbon nanotube coupled pi-surface modes utilising electron energy-loss spectra acquired using a STEM/Enfina system.

Numerous studies have utilised electron energy-loss (EEL) spectra acquired in the plasmon (2-10 eV) regime in order to probe delocalised pi-electronic states of multi-wall carbon nanotubes (MWCNTs). Interpretation of electron energy loss (EEL) spectra of MWCNTs in the 2-10 eV regime. Carbon (accepted for publication); Blank et al. J. Appl. Phys. 91 (2002) 1657). In the present contribution, EEL spectra were acquired from a 2D raster defined on a bottle-shaped MWCNT, using a Gatan UHV Enfina system attached to a dedicated scanning transmission electron microscope (STEM). The technique utilised to isolate and sequentially filter each of the volume and surface resonances is described in detail. Utilising a scale for the intensity of a filtered mode enables one to 'see' the distribution of each resonance in the raster. This enables striking 3D resonance-filtered spectrum images (SIs) of pi-collective modes to be observed. Red-shift of the lower energy split pi-surface resonance provides explicit evidence of pi-surface mode coupling predicted for thin graphitic films (Lucas et al. Phys. Rev. B 49 (1994) 2888). Resonance-filtered SIs are also compared to non-filtered SIs with suppressed surface contributions, acquired utilising a displaced collector aperture. The present filtering technique is seen to isolate surface contributions more effectively, and without the significant loss of statistics, associated with the displaced collector aperture mode. Isolation of collective modes utilising 3D resonance-filtered spectrum imaging, demonstrates a valuable method for 'pinpointing' the location of discrete modes in irregularly shaped nanostructures.