Atom force microscopy study on HTHP as-grown diamond single crystals

For understanding the mechanism of diamond growth at high temperature–high pressure (HTHP) from a metallic catalyst–graphite system, it is of great interest to perform atomic force microscopy (AFM) experiments, which provide a unique technique different from that of normal optical and electronic microscopy studies, to study the topography of HTHP as-grown diamond single crystals. In the present paper, we report first AFM results on diamond single crystals grown from a Fe-Ni-C system at HTHP to reveal the growth mechanism of diamond single crystals at HTHP. AFM images for as-grown diamond samples show dark etch pits on the (111) surface, indicating dislocations. Some fine particles about 100–300 nm in dimension were directly observed on the (100) diamond surface. These particles are believed to have been formed through transition of graphite to diamond under the effect of the catalyst and to have been transported to the growing diamond surface through a metallic thin film by diffusion. The roughness of the (100) diamond surface is found to be about several tens of nanometers through profile analysis. The diamond growth at HTHP, in a sense, could be considered as a process of unification of these fine diamond particles or of carbon-atom-cluster recombination on the growing diamond crystal surface. Successive growth interlayer steps on the (111) diamond surface were systemically examined. The heights of the growth interlayer steps were measured by sectional analysis. It was shown that the heights of the growth interlayer steps are quite different and range from about 10 to 25 nm. The source of the interlayer steps might be dislocations. The diamond-growth mechanism at HTHP could be indicated by the AFM topography of the fine diamond particles and the train-growth interlayer steps on the as-grown diamond surfaces. Received: 29 March 2001 / Accepted: 20 August 2001 / Published online: 2 October 2001     

Two-photon-excited luminescence spectra in diamond nanocrystals

Two-photon-excited luminescence (TEL) spectra have been recorded in the blue (400–500 nm) and near-ultraviolet (300–400 nm) ranges for diamond particles with 4 nm average size, which were obtained by detonation synthesis from explosives. The observed TEL bands are attributed, by comparing the obtained spectra with the impurity luminescence spectra in large diamond crystals, to N2 and N3 defects associated with the presence of nitrogen impurities in diamond. The TEL spectra presented are found to have certain distinguishing features: short-wavelength shift of the maximum and changes in the shape and width of the spectral bands for ultradispersed diamond compared with the spectrum in bulk crystals. Fiz. Tverd. Tela (St. Petersburg) 41, 1110–1112 (June 1999)     

Inversion of the electron spin resonance signal from a P1 center in a synthetic diamond crystal

We have studied the electron spin resonance (ESR) of a 0.59 carat synthetic diamond single crystal at room temperature. The crystal was grown on a “split-sphere” apparatus in the Fe-Ni-C system by the temperature gradient method. After high-temperature/high-pressure treatment of the diamond, it was observed that as the microwave power supplied to the sample increased from 70 μW to 70 mW in an H₁₀₂ cavity, the ESR signal from the P1 center (a nitrogen atom substituting for carbon at a lattice point of the diamond crystal: C-form nitrogen) is inverted. In the original diamond (before high-temperature/high-pressure treatment), no inversion of the ESR signal was observed. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 9–12, January–February, 2006.     

Photoacoustic spectroscopy of diamond powders and polycrystalline films

Photoacoustic spectroscopy is used to study optical absorption in diamond powders and polycrystalline films. The photoacoustic spectra of diamond powders with crystallite sizes in the range from ∼100 μm to 4 nm and diamond films grown by chemical vapor deposition (CVD) had a number of general characteristic features corresponding to the fundamental absorption edge for light with photon energies exceeding the width of the diamond band gap (∼5.4 eV) and to absorption in the visible and infrared by crystal-structure defects and the presence of non-diamond carbon. For samples of thin (∼10 μm) diamond films on silicon, the photoacoustic spectra revealed peculiarities associated with absorption in the silicon substrate of light transmitted by the diamond film. The shape of the spectral dependence of the amplitude of the photoacoustic signal in the ultraviolet indicates considerable scattering of light specularly reflected from the randomly distributed faces of the diamond crystallites both in the polycrystalline films and in the powders. The dependence of the shape of the photoacoustic spectra on the light modulation frequency allows one to estimate the thermal conductivity of the diamond films, which turns out to be significantly lower than the thermal conductivity of single-crystal diamond. Fiz. Tverd. Tela (St. Petersburg) 39, 1787–1791 (October 1997)     

Optical and paramagnetic properties of natural diamonds implanted with hydrogen ions

We used IR spectroscopy and electron spin resonance (ESR) to investigate defect reconstruction processes occurring in diamond crystals due to their implantation with H⁺ ions with energies of 65–350 keV and subsequent isochronous annealing in the temperature range 250–1550°C. We found that most of the hydrogen in diamonds implanted with protons is in an IR-inactive state. Magnetic hysteresis related to radiation defects in diamond is observed for the first time at room temperature using ESR. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 4, pp. 485–490, July–August, 2007.     

Synthesis of platinum and platinum–ruthenium-modified diamond nanoparticles

With the aim of developing dimensionally stable-supported catalysts for direct methanol fuel cell application, Pt and Pt–Ru catalyst nanoparticles were deposited onto undoped and boron-doped diamond nanoparticles (BDDNPs) through a chemical reduction route using sodium borohydride as a reducing agent. As-received commercial diamond nanoparticles (DNPs) were purified by refluxing in aqueous nitric acid solution. Prompt gamma neutron activation analysis and transmission electron microscopy (TEM) techniques were employed to characterize the as-received and purified DNPs. The purified diamond nanoparticulates, as well as the supported Pt and Pt–Ru catalyst systems, were subjected to various physicochemical characterizations, such as scanning electron microscopy, energy dispersive analysis, TEM, X-ray diffraction, inductively coupled plasma-mass spectrometry, X-ray photoelectron spectroscopy, and infrared spectroscopy. Physicochemical characterization showed that the sizes of Pt and Pt–Ru particles were only a few nanometers (2–5 nm), and they were homogeneously dispersed on the diamond surface (5–10 nm). The chemical reduction method offers a simple route to prepare the well-dispersed Pt and Pt–Ru catalyst nanoparticulates on undoped and BDDNPs for their possible employment as an advanced electrode material in direct methanol fuel cells.     

Mounting-induced strains in red-emitting (Al)InGaP laser diodes tuned by pressure

The hydrostatic pressure behavior of red-emitting diode lasers packaged on Si, AlN, and diamond submounts is studied in the 0–2 GPa range by emission and photocurrent spectroscopy. Photocurrent spectroscopy allows for simultaneous measurement of the InGaP quantum well and (Al_0.5Ga_0.5)_0.5In_0.5P waveguide. A broadening of the absorption edge of the waveguide is observed for all devices and explained by the pressure-induced direct-to-indirect transition in this material. For the QW resonance, distinct differences are observed for differently packaged devices. Thus, very low pressure tuning rates are demonstrated for devices packaged on diamond and AlN submounts and explained by the presence of shear strain components. Consistently we find the device packaged on Si to be least affected by the strain caused by the pressure cycling.     

The dynamic symmetry and plastic deformation of diamond lattice

An analysis of possible transformations of moments of force by a diamond lattice has been made. The conditions of resonance transformations of moments of force by this lattice have been found. The dynamics symmetry of the diamond lattice has been determined in terms of the Shubnikov group Fd3m'. Besides, it has been found that resonance librationally deformed configurations are oneperiodic and have cores 〈110〉 two times more deformed than the surrounding area. As a result of the action of resonance phonons of the librational mode it is possible to generate a new kind of defects-bidislocations with Burgers vector components+[110]/2 and −[110]/2. It has been shown that bidislocations can play an essential role in plastic deformation of a diamond lattice and other related lattices.     

Ion-implanted buried layer in diamond as a source of ballistic phonons at liquid-helium temperatures

It is shown that an approximately 150 nm thick ion-implanted buried layer in diamond and excited by a pulsed laser at wavelength λ=337 nm is a source of nonequilibrium acoustic phonons propagating ballistically through the diamond sample at temperatures ∼2 K. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 4, 270–272 (25 August 1996)     

Comparison of optical properties and mechanical/electrical degradation of some low density polyethylene-and polypropylene-based polymer blends

In this study, the optical properties as well as mechanical and electrical degradation of low-density polyethylene (LDPE)/polypropylene fiber (PP fiber) (10–50% PP fiber), polypropylene (PP)/PP fiber (10–50% PP fiber), and LDPE/diamond (0.1–3% diamond) blends, which are prepared by hot pressing method, with changing thicknesses ranging from 30 to 225 μm, are compared. The spectra, in the wavelength range 200–2500 nm, are examined. Based on optical absorption spectra obtained, Tauc graphs are plotted. Determined values of the direct optical energy gap (E _d ^opt ), the indirect optical energy gap (E _i ^opt ), the width of the band (ΔE), and ultraviolet transmittance (T_UV) are listed. The direct E _d ^opt and indirect E _i ^opt values for organic blends are in the range of 3.10–3.17 eV and 1.52–2.99 eV; for inorganic blends they are 1.80–4.13 eV and 1.55–4.7 eV respectively. The electrical strength (ε) and the mechanical tension (σ) have been investigated, and graphs (the dependence of the electrical life time log τ_ε on ε) are given. The experimental results are analyzed from the viewpoint of the validity of the thermofluctuation theory. LDPE and LDPE/0.5% diamond composite parameters consecutively changed: σ from 68 to 82 MPa, ε from 60·10⁶ to 85·10⁶ V/m, mechanical lifetime τ_σ from 10 to 1.5·10⁵ sec, electrical lifetime τ_ε from 2· 10³ to 2·10⁵ sec, and structure-sensitive parameters γ and χ — from 1.48 to 1.18 (J)MPa/mole and from 0.97 to 0.70 (J)Vm⁻¹/mole respectively. The values of mechanical and electrical durability were observed to increase by 20 and 41%, respectively, for LDPE/0.5% diamond composite. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 677–683, September–October, 2007.     

Mechanism of the formation of a diamond nanocomposite during transformations of C60 fullerite at high pressure

The results of an investigation of the transformation of C₆₀ fullerite to diamond under pressure through intermediate three-dimensionally polymerized and amorphous phases are reported. It is found that treatment of fullerite C₆₀ at pressures 12–14 GPa and temperatures ∼1400°C produces a nanocrystalline graphite-diamond composite with a concentration of the diamond component exceeding 50%. At lower temperatures (700–1200°C) nanocomposites consisting of diamondlike (sp ³) and graphitic (sp ²) amorphous phases are formed. The nanocomposites obtained have extremely high mechanical characteristics: hardness comparable to that of best diamond single crystals and fracture resistance two times greater than that of diamond. Mechanisms leading to the transformation of C₆₀ fullerite into diamond-based nanocomposites and the reasons for the high mechanical characteristics of these nanocomposites are discussed. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 11, 822–827 (10 June 1999)     

Proposal on the measurements of d–p elastic scattering analyzing powers at 0.3–2.0 GeV at the Internal Target Station of the Nuclotron

A new high-energy beam polarimeter is proposed for Nuclotron, which uses the Internal Target Station (ITS). This polarimeter based on a measurement of asymmetry for the d–p elastic scattering will allow one to measure simultaneously both vector and tensor components of deuteron beam polarization. For this purpose an analyzing powers measurement for the d–p elastic scattering at energies T _d = 0.88–2 GeV is proposed. The precise measurements of the deuteron analyzing powers over the energy range T _d = 300–2000 MeV can give an irreplaceable clue to the study of the spin dependence of three nucleon forces. The text was submitted by the authors in English.     

Novel technique for hetero-epitaxial diamond film growth on cubic boron nitride from iron carbide at high temperature and high pressure

Cubic boron nitride (c-BN) crystals about 0.1–0.3 mmin dimension were treated with iron carbide powders (high purity 99%) with size of 80–100 mesh at a high temperature of 1620 K and a high pressure of 5.2 GPa. It was found that hetero-epitaxial diamond films have been grown on the c-BN from iron carbide. The formation of dia-mond films on the cubic boron nitride can be confirmed by laser Raman spectra, face scan of elements and reflective high-energy electron diffraction. It was suggested that diamond films could be epitaxially formed on the c-BN through decomposition of iron carbide. This approach provides a possible and very effective way to realize hetero-epitaxial growth of homogeneous and large-area diamond films on c-BN, which is different from the conventional technique using a chemical vapor deposition method. Received: 20 December 2000 / Accepted: 9 January 2001 / Published online: 28 February 2001     

Laser polishing of diamond plates

Results are reported on laser polishing of 150–400-μm-thick free-standing diamond films with either a copper vapor laser (510 nm wavelength) or an ArF excimer laser (193 nm wavelength). Studies were focused on three particular goals. First, we aimed at a choice of optimum conditions for laser polishing of thick diamond films. It was shown that the laser polishing conditions and the resulting surface roughness were controlled by varying the angle of incidence of a scanning laser beam and by polishing time. Second, the laser ablation technique was applied to remove a defective layer from the “substrate” side of the diamond plates in order to reduce optical losses due to absorption in this layer. Third, the structure of the laser-graphitized diamond surface was studied using UV, visible, and IR optical spectroscopy techniques in the course of the “step-by-step” oxidative removal of the graphitic layer with increasing temperature of the oxidation in ambient air. Once the graphitic layer was removed, the optical transmission in the UV-visible-IR spectral range of the diamond films polished under optimum conditions was measured and compared with the optical transmission of the mechanically polished diamond films. It was shown that the optical quality (in the long-wave infrared region) of the laser-polished diamond plates was sufficient to reach the transmittance value very close to the theoretical limit. Received: 20 October 1998 / Accepted: 8 March 1999 / Published online: 5 May 1999     

Spectral and kinetic characteristics of the pulsed cathodoluminescence of a natural IIa-type diamond

Emission spectra and decay kinetics of pulsed cathodoluminescence of a natural IIa-type diamond sample are investigated in the spectral range 340–680 nm. The luminescence of the vibronic N3-system and band A are observed. The N3-system is dominant on a nanosecond scale and has a 415.2-nm zero-phonon line with phonon replicas in the range 430–460 nm. The decay time for the N3 system is found to be 30–50 ns. Structureless band A is observed on a millisecond scale; it has a maximum at 460 nm and a decay time of 8.5–8.8 ms. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 53–57, January, 2007.     

Comparison of models and lattice-gas simulations for Liesegang patterns

For more than a century Liesegang patterns – self-organized, quasi-periodic structures occurring in diffusion-limited chemical reactions with two components – have been attracting scientists. The pattern formation can be described by four basic empirical laws. In addition to many experiments, several models have been devised to understand the formation of the bands and rings. Here we review the most important models and complement them with detailed three-dimensional lattice-gas simulations. We show how the mean-field predictions can be reconciled with experimental data by a redefinition of the distances suggested by our lattice-gas simulations.     

Spectral components that form UV absorption spectrum of Ce3+ and Ce(IV) valence states in matrix of photothermorefractive glasses

We have measured the UV absorption spectra of photothermorefractive glasses of the system Na₂O-ZnO-Al₂O₃-NaF-SiO₂ doped by cerium oxide in the range of (2.8–5.0) × 10⁴ cm⁻¹ (360–200 nm). The spectra have been processed by the method of dispersion analysis based on the analytical convolution model for the complex dielectric function of glasses. We show that the absorption band centered at 3.3 × 10⁴ cm⁻¹ (∼303 nm) that is attributed to the transition 2F _5/2 → 5d in the Ce³⁺ ion, is an envelope of three spectral components. The broad absorption range (3.5–4.7) × 10⁴ cm⁻¹ (200–270 nm) that is commonly interpreted as a charge transfer band of the Ce(IV) valence state, is an envelope of at least three spectral components.     

Superconductivity in covalent semiconductors

This review covers recent advances in superconductivity of diamond, Si, SiC, group III–V and II–IV semiconductors, metal-intercalated graphite and fullerites. The results are critically analyzed and prospects are given for future research directions. In particular, it is argued that the highest transition temperatures of ∼9 K in diamond and 11.5 K in CaC₆ can further be enhanced and that no reliable evidence exists yet for superconductivity in III-V semiconductors.      

Pressure dependence of the lattice constant of diamond: Isotopic effects

The pressure dependence of lattice constants of ¹³C-enriched diamond and diamond of natural isotopic composition have been studied by using x-ray synchrotron radiation and the imaging plate technique. The compression curves reveal features which indicate an inversion of the isotope effect at high pressure. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 2, 73–77 (25 January 1996) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Determination of the thermal conductivity of polycrystalline diamond films by means of the photoacoustic effect

A new method of determining the heat-conducting properties of diamond films is proposed, based on the photoacoustic effect. This method is used to study diamond polycrystalline films grown on silicon by chemical vapor deposition in a microwave discharge plasma. The thermal conductivity obtained was approximately half that for single-crystal diamond. Zh. Tekh. Fiz. 69, 97–101 (April 1999)