Synthesis of nano-polycrystalline diamond from glassy carbon at pressures up to 25 GPa

ABSTRACT

Nano-polycrystalline diamond (NPD) with various grain sizes has been synthesized from glassy carbon at pressures 15–25?GPa and temperatures 1700–2300°C using multianvil apparatus. The minimum temperature for the synthesis of pure NPD, below which a small amount of compressed graphite was formed, significantly increased with pressure from ～1700°C at 15?GPa to ～1900°C at 25?GPa. The NPD having grain sizes less than ～50?nm was synthesized at temperatures below ～2000°C at 15?GPa and ～2300°C at 25?GPa, above which significant grain growth was observed. The grain size of NPD decreases with increasing pressure and decreasing temperature, and the pure NPD with grain sizes less than 10?nm is obtained in a limited temperature range around 1800–2000°C, depending on pressure. The pure NPD from glassy carbon is highly transparent and exhibits a granular nano-texture, whose grain size is tunable by selecting adequate pressure and temperature conditions.     

Effect of deuterium on phase transformations in fullerenes at high temperatures and high pressures

The effect deuterium has on phase transformations is studied for amorphous and crystalline fullerenes C₆₀ and C₇₀ at high temperatures of up to 1300°C and high pressures (2–8 GPa). Amorphous fullerene phases are obtained via long grinding in a planetary mill. Structure is studied by means of neutron diffraction. In all cases, amorphous graphite (nanographite) forms in the temperature range of 800–1100°C. This material has different diffraction spectra distinguished by the heights of the halos observed on the graphite diffraction maxima and their relative intensities. These spectra (the structure of nanographite) are affected by preliminary amorphization, the number of carbon atoms in the fullerenes (C60 or C70), and the introduction of deuterium atoms. The different spectra of amorphous (disordered) graphite testify to its varying structure.     

Structural transformations of the cumulene form of amorphous carbyne at high pressure

Structural transformations of the cumulene form of amorphous carbyne which are induced by heating at high pressure (7.7 GPa) are investigated. These can be described by the sequence amorphous phase — crystal — amorphous phase — disordered graphite. Raman scattering shows that predominately the chain structure of carbyne remains at the first three stages. It was found that the intermediate crystalline phase is an unknown modification of carbon whose structure is identified as cubic (a=3.145 Å). A mechanism of structural transformations in carbyne that involves the formation of new covalent bonds between chains is discussed. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 4, 237–242 (25 August 1997)     

Structure and mechanical properties of low stress tetrahedral amorphous carbon films prepared by pulsed laser deposition

Tetrahedral amorphous carbon films have been produced by pulsed laser deposition, at a wavelength of 248 nm, ablating highly oriented pyrolytic graphite at room temperature, in a 10^-2 Pa vacuum, at fluences ranging between 0.5 and 35 Jcm^-2. Both (100) Si wafers and wafers covered with a SiC polycrystalline interlayer were used as substrates. Film structure was investigated by Raman spectroscopy at different excitation wavelength from 633 nm to 229 nm and by transmission Electron Energy Loss Spectroscopy. The films, which are hydrogen-free, as shown by Fourier Transform Infrared Spectroscopy, undergo a transition from mainly disordered graphitic to up to 80% tetrahedral amorphous carbon (ta-C) above a threshold laser fluence of 5 J cm^-2. By X-ray reflectivity roughness, density and cross-sectional layering of selected samples were studied. Film hardness as high as 70 GPa was obtained by nanoindentation on films deposited with the SiC interlayer. By scratch test film adhesion and friction coefficients between 0.06 and 0.11 were measured. By profilometry we obtained residual stress values not higher than 2 GPa in as-deposited 80% sp³ ta-C films. Received 25 June 2001     

High-Pressure Raman Study of Zincblende,Cinnabar, and Cmcm Phases Of ZnTe

Raman measurements of ZnTe have been performed at pressures up to 15 GPa. Frequencies, line widths, and intensities of first- and second-order Raman features of the zincblende phase (0-9.5 GPa) were studied in detail. In this note, we focus on the Raman spectra of the high-pressure cinnabar and Cmcm phases. In the transition regime from cinnabar to Cmcm (12.2 to 13.7 GPa) the Raman data indicate the possible existence of a new intermediate high-pressure phase.     

Observation of Raman band shifting with excitation wavelength for carbons and graphites

The Raman spectra of crystalline graphite, graphite damaged by ion-etching, and structurally disordered pyrolytic and glassy carbons were examined as a function of excitation wavelength λ over the range 488.0 to 647.1 nm. The bands located at 1360, 2720 and 2950 cm ¹ with λ = 488.0 nm undergo a progressive red-shift as λ increases, while the positions of the other major bands (1580 and 1620 cm ¹) are invariant. The significance of these observations is briefly discussed.     

The structure of thin carbon films deposited at 13.5 nm EUV irradiation

In this work, the structure and chemistry of thin nm-thick carbon films deposited on a substrate using strong 13.5 nm EUV irradiation under a strong vacuum were studied. The film structure was studied by Raman spectroscopy in comparison with the Raman spectra of well-known carbon phases: diamond, single-wall nanotubes, nano- and micro-crystalline graphite and amorphous carbon. As well, FTIR spectroscopy was used to study possible IR-active chemical bonds, primarily, hydrogen bonds. It was shown that films deposited on a surface under EUV irradiation consists of amorphous sp ²-carbon. The mechanisms of deposition are discussed briefly. Knowledge about the structure and chemistry of such carbon films is very important for EUV lithography.     

Phase transformations in amorphous fullerite C60 under high pressure and high temperature

First phase transformations of amorphous fullerite C₆₀ at high temperatures (up to 1800 K) and high pressures (up to 8 GPa) have been investigated and compared with the previous studies on the crystalline fullerite. The study was conducted using neutron diffraction and Raman spectroscopy. The amorphous fullerite was obtained by ball-milling. We have shown that under thermobaric treatment no crystallization of amorphous fullerite into С₆₀ molecular modification is observed, and it transforms into amorphous-like or crystalline graphite. A kinetic diagram of phase transformation of amorphous fullerite in temperature–pressure coordinates was constructed for the first time. Unlike in crystalline fullerite, no crystalline polymerized phases were formed under thermobaric treatment on amorphous fullerite. We found that amorphous fullerite turned out to be less resistant to thermobaric treatment, and amorphous-like or crystalline graphite were formed at lower temperatures than in crystalline fullerite.     

High pressure raman study of PbMoO4

Abstract

Raman spectra of PbMoO₄ have been measured up to 31 GPa in a diamond anvil cell (DAC). Two new phases were found at 10 and 16 GPa pressures at room temperature.     

High-pressure Raman and infrared study of ZrV 2O7

The room-temperature Raman and infrared spectra of zirconium vanadate (ZrV ₂O₇) were observed up to pressures of 12 GPa and 5.7 GPa, respectively. The frequencies of the optically active modes at ambient pressure were calculated using direct methods and compared with experimental values. Average mode Grüneisen parameters were calculated for the Raman and infrared active modes. Changes in the spectra under pressure indicate a phase transition at ∼1.6 GPa, which is consistent with the previously observed α (cubic) to β (pseudo-tetragonal) phase transition, and changes in the spectra at ∼4 GPa are consistent with an irreversible transformation to an amorphous structure.     

RAMAN AND INFRARED SPECTRA OF IODOFORM AT HIGH PRESSURES

ABSTRACT

Raman and infrared spectra are reported for iodoform samples in diamond anvil cells at ambient temperature and at pressures up to 5 GPa (Raman) and 10 GPa (infrared). The spectra appear to evolve smoothly and no evidence of any structural phase transitions is found. The dependence on pressure of 7 Raman and 13 infrared peak wavenumbers is presented. A large increase in intermolecular bonding strengths is confirmed, together with a moderate increase in intramolecular I-C-I bending forces. Color changes in the samples at high pressures are found to be mostly reversible, but long exposure to high fluxes of visible photons causes some molecular dissociation, with the release of iodine.     

Phase transitions of sulfur at high pressure: Influence of temperature and pressure environment

Abstract

Phase transitions of orthorhombic sulfur were investigated above 10 GPa by Raman spectroscopy using red light excitation. Transitions into several phases that have been reported in previous studies using green light excitation, are confirmed. The phase behaviour is observed to depend strongly on the preparation method. In the presence of a pressure transmitting medium (methanol/ethanol, 4:1), a sequence of phases α-S₈ → [intermediate phase (“ip”) + S₆] → [S₆ + high pressure-low temperature phase (“hplt”)] is described and characterized. Without the use of a pressure transmitting medium, the phase sequence α-S₈ → [“ip” + “hplt”] + “hplt” is observed. In addition, contributions of amorphous sulfur are detected around 10 GPa, i.e. at pressures below the transformation of α-S₈ into the above-mentioned phases. Characteristic Raman spectra of the different phases are extracted and documented over a wide pressure range.     

Shock-wave studies of anomalous compressibility of glassy carbon

The physico-mechanical properties of amorphous glassy carbon are investigated under shock compression up to 10 GPa. Experiments are carried out on the continuous recording of the mass velocity of compression pulses propagating in glassy carbon samples with initial densities of 1.502(5) g/cm³ and 1.55(2) g/cm³. It is shown that, in both cases, a compression wave in glassy carbon contains a leading precursor with amplitude of 0.135(5) GPa. It is established that, in the range of pressures up to 2 GPa, a shock discontinuity in glassy carbon is transformed into a broadened compression wave, and shock waves are formed in the release wave, which generally means the anomalous compressibility of the material in both the compression and release waves. It is shown that, at pressure higher than 3 GPa, anomalous behavior turns into normal behavior, accompanied by the formation of a shock compression wave. In the investigated area of pressure, possible structural changes in glassy carbon under shock compression have a reversible character. A physico-mechanical model of glassy carbon is proposed that involves the equation of state and a constitutive relation for Poisson’s ratio and allows the numerical simulation of physico-mechanical and thermophysical properties of glassy carbon of different densities in the region of its anomalous compressibility.     

Raman scattering and phase changes of CulnSe2 and LiInSe2 at high pressure

Abstract

We have investigated the effect of pressure on the Raman spectra of the ternary chalcogenides CulnSe₂ (chalcopyrite structure) and LiInSe₂ (β-NaFeO₂ structure) for pressures extending well above their first pressure-induced phase transitions. Sign and magnitude of Griineisen parameters are discussed by comparing to related tetrahedrally coordinated chalcogenides. Discontinuous changes of the Raman frequencies indicate pressure-induced phase transitions at 8.0±0.3 and 4.2±0.2 GPa in CuInSe₂ and in LiInSe₂, respectively. The Raman spectra of the low-pressure phases are not recovered after pressure release but a highly disordered structure is induced. In the case of LiInSe₂, the effect of laser heating on the Raman spectra of the high-pressure phase is investigated and discussed in light of recent high-pressure x-ray investigations.     

Infrared Spectra of Liquid and Crystalline Ethanol at High Pressures

Abstract

Mid-infrared spectra in the ranges 400–1800 and 2700–4600 cm^?1 of ethanol samples in diamond anvil cells at ambient temperature and pressures up to 11 GPa are reported. The freezing pressure is confirmed to be 1.8 GPa, and, unlike methanol, the resulting solid is crystalline rather than glassy. No further phase transitions are observed in this pressure range. The wave number shifts of 30 selected peaks with pressure are deduced, and their small magnitudes indicate that only minor distortions of the molecules occur. The effects of the strengthening of the intermolecular hydrogen bonds with pressure on the internal modes are briefly discussed.     

High pressure Raman studies on solid iodine

Abstract

Raman spectra of solid iodine were measured up to 27 GPa. Additional bands, whch appear above 10 GPa, are discussed with respect to a quasi one dimensional molecular phase existing at intermediate pressures and may indicate a more subtle way of molecular dissociation than previously suggested. Higher order spectra due to two-and three phonon processes involving internal and external modes were observed up to 10 GPa.     

Amorphous diamond: a high-pressure superhard carbon allotrope

Compressing glassy carbon above 40 GPa, we have observed a new carbon allotrope with a fully sp(3)-bonded amorphous structure and diamondlike strength. Synchrotron x-ray Raman spectroscopy revealed a continuous pressure-induced sp(2)-to-sp(3) bonding change, while x-ray diffraction confirmed the perseverance of noncrystallinity. The transition was reversible upon releasing pressure. Used as an indenter, the glassy carbon ball demonstrated exceptional strength by reaching 130 GPa with a confining pressure of 60 GPa. Such an extremely large stress difference of >70 GPa has never been observed in any material besides diamond, indicating the high hardness of this high-pressure carbon allotrope.     

Tip-Enhanced Raman Spectroscopy and Mapping of Graphene Sheets

Abstract: Single graphene sheets, a few graphene layers, and bulk graphite, obtained via both micromechanical cleavage of highly oriented pyrolytic graphite and carbon vapor deposition methods, were deposited on a thin glass substrate without the use of any chemical treatment. Micro-Raman spectroscopy, tip-enhanced Raman spectroscopy (TERS), and tip-enhanced Raman spectroscopy mapping (TERM) were used for characterization of the graphene layers. In particular, TERM allows for the investigation of individual graphene sheets with high Raman signal enhancement factors and allows for imaging of local defects with nanometer resolution. Enhancement up to 560% of the graphene Raman band intensity was obtained using TERS. TERM (with resolution better than 100 nm) showed an increase in the number of structural defects (D band) on the edges of both graphene and graphite regions.     

On the formation of photoinduced high pressure phases in sulfur below 10 GPa

Abstract

We investigate the phase transformations in sulfur for pressures up to 10 GPa by time resolved Raman spectroscopy. The transition to the photosensitive phase p-S is stimulated by the blue laser line between 3 and 9 GPa. The kinetics of this transition as derived from the time evolution of the intensities of characteristic Raman excitations shows the typical features of an activated first order phase transition. This transformation proceeds via a disordered (amorphous) intermediate state.

Above 9 GPa a further phase change to S, is kinetically characterized and follows similar rules i.e. the integral intensities of selected S, Raman lines exhibit a sigmoidal time dependence. In both high pressure phases a broad Raman excitation between 800 and 1000 cm^?1 is observed.     

Energy spectrum and phase transitions in C70 fullerite crystals at high pressure

Measurements have been made of the Raman, optical absorption, and luminescence spectra of single crystals and pellets of the fullerite C₇₀ at T=300 K and at pressures up to 12 GPa. The baric shift dω/dP and the Grüneisen parameters of the Raman-active intramolecular phonon modes have been determined. It has been established that the d ω/dP value for certain phonon modes abruptly changes at pressures of P ₁≈2 GPa and P ₂≈5.5 GPa, as do the half-widths of the Raman lines. These features in the Raman spectrum are associated with phase transitions at high pressure. The baric shifts of the absorption and luminescence edges of C₇₀ crystals have been determined and are −0.12 eV/GPa and −0.11 eV/GPa, respectively, for absorption and luminescence. The baric shift of the absorption edge decreases significantly with increasing pressure and is −0.03 eV/GPa at 10 GPa. These data have been used to determine the deformation potential of the fullerite C₇₀, which is about 2.1±0.1 eV. Zh. éksp. Teor. Fiz. 111, 262–273 (January 1997)