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ATEM-EELS study of new diamond-like phases in the BCN system

Falko Langenhorsta and Vladimir L. Solozhenkob
a

Bayerisches Geoinstitut, Universitat Bayreuth, 95440 Bayreuth, Germany. E-mail: Falko.Langenhorst@uni-bayreuth.de Institute for Superhard Materials of the National Academy of Sciences of Ukraine, Kiev 04074, Ukraine

Received 9th July 2002, Accepted 16th August 2002 First published as an Advance Article on the web 17th September 2002

Novel ternary diamond-like phases of the BCN system were synthesized at pressures up to 30 GPa and temperatures up to 3500 K by static and dynamic compression of graphite-like BNC solid solutions. The structure and properties of these new phases were studied using analytical transmission electron microscopy (ATEM), electron energy loss spectroscopy (EELS) and powder X-ray diraction. Our results reveal that B, C and N atoms are homogeneously distributed over the crystal lattices of the BCN phases under study without forming superstructures. All ternary diamond-like BCN phases indicate a clear tendency to decompose at high temperatures because of supersaturation of diamond in the BN component.

Introduction
The similar atom sizes and the similar structures of boron nitride and carbon polymorphs (i.e. cubic BN (cBN) and diamond, or hexagonal graphite-like BN (hBN) and graphite) suggest that it might be possible to synthesize phases containing all three elements. While several low-density graphite-like phases containing B, C, and N have been reported (see e.g., ref. 1), there is less information on the synthesis of dense phases containing all three elements.26 Such diamond-like ternary phases are highly desirable as they might combine the best properties of the elemental or binary compounds of the BCN system. For example, a cBNdiamond alloy should be thermally more stable and resistant to oxidation, less reactive with iron than pure diamond, and harder than cubic boron nitride. However, the data on the synthesis of diamond-like BCN phases reported in ref. 26 are rather contradictory. Despite the experimental eorts, the physical properties of these materials have not been well characterized, nor is their crystal structure known. To date it is unclear whether the synthesis products are diamond-like solid solutions between carbon and boron nitride or just mechanical mixtures of highly dispersed diamond and cBN. Very recently the cubic BC2N, a new superhard phase, and diamond-like BNC solid solutions have been synthesized at high pressures and temperatures by Solozhenko et al.7,8 Here, we report the results of detailed ATEM-EELS studies of some new diamond-like ternary phases in the BCN system.

very close to (BN)0.5C0.5 we will later refer to this phase as graphite-like gBC2N. Synthesis at static pressures Diamond-like BCN ternary phases were synthesized according to Solozhenko et al.7 by direct solid-state phase transition of graphite-like BC2N at 25 GPa and temperatures of $2100 K and $2300 K (annealing times: 60 and 30 s, respectively) using a large-volume multianvil system (MA) and a Sumitomo 1200 ton press at the Bayerisches Geoinstitut. The 10/4 mm cell assembly,10 composed of eight WC cubes with 4 mm truncations, a MgO octahedron of 10 mm edge length, and a LaCrO3 furnace, was used. The sample was placed into a Pt capsule. Temperature was measured using a W3%ReW25%Re thermocouple without corrections for the pressure eect on the thermocouple emf. Particularly at the high temperatures achieved in this study, the uncertainty in the exact temperature value is considerable due to the substantial temperature gradient along the sample axis. The thermocouple measures at one end of the sample, whereas the observations are done in the center of the sample, where temperatures are usually 100 to 200 K higher. This temperature correction has been taken into account in Table 1. The sample pressure at high temperatures was calibrated as a function of hydraulic oil pressure using phase diagrams of MgSiO3 and Mg2SiO4 . High-pressure phase transitions of gBC2N at temperatures above 2500 K were studied using a laser-heated diamond anvil cell (DAC) at beamline ID30, European Synchrotron Radiation Facility. Shockcompression synthesis The isoentropic shockcompression (SC) synthesis of diamond-like BNC solid solution was carried out at 30 GPa using gBC2N in cylindrical recovery containers with a ring gap11 that allowed concentration of explosion energy in a given direction and multiple reections of shock waves at the walls of the container. The incident shock pressure on the sample is governed by the type of high-explosive (RDXANFO or Phys. Chem. Chem. Phys., 2002, 4, 51835188 This journal is # The Owner Societies 2002 5183

Experimental
Starting materials A nanopowder of turbostratic graphite-like (BN)0.48C0.52 solid solution was used as the starting material for the synthesis of diamond-like BCN phases. The precursor was synthesized by simultaneous nitridation of boric acid and carbonization of saccharose in molten urea followed by annealing in nitrogen at 1770 K.9 Since the stoichiometry of the starting material is DOI: 10.1039/b206691b

Table 1 Synthesis conditions, compositions and lattice parameters a of the diamond-like cubic BCN phases and the graphite-like BC2N precursor. Most lattice parameters are based on electron diraction patterns Sample gBC2N cBC2N cBC3N cBC3N cBC8N
a

Experimenta SC MA MA DAC

P,T,t-conditions 30 20 20 30

B (atom %) 24.9 26.8 21.9 20.5 9.5

b

C (atom %) 51.7 46.6 57.2 59.4 79.5 X-ray diraction data.

N (atom %) 23.4 26.6 20.9 20.1 11.0

a (A) 3.600(10) 3.593(4)b 3.603(10) 3.611(6)b 3.582(10) 3.572(10)

GPa, GPa, GPa, GPa,

$3500 $2300 $2100 $3000

K, 1ms K, 30 s K, 60 s K 180 s

SC Shockcompression; MA Multi-anvil; DAC Diamond anvil cell.

RDXNobelit 100 compositions). The use of the special additive that is characterized by a high shock temperature and a high compressibility, allowed heating of the sample up to 3500 K, and its abrupt cooling ($108 K s1) on decompression. The recovered samples were immersed in hydrochloric acid to dissolve an additive, then heated in concentrated HClO4 to remove unchanged starting material. X-ray diraction Samples synthesized in multianvil experiments were studied using a Rigaku powder microdiractometer (Cr-Ka-radiation, l 2.2910 A) and energy-dispersive X-ray diraction with synchrotron radiation at beamline F2.1, HASYLAB (see ref. 12). Powder X-ray diraction patterns of recovered samples produced in shockcompression experiments were taken in the back-reection mode using a D5000 SIEMENS diractometer (Cu-Ka-radiation, l 1.54184 A). Data were collected from   20 to 100 2y in steps of 0.02 ; the counting time was 10 s at each step. A high purity silicon standard was used to adjust the goniometer. The diraction patterns were evaluated using the GSAS software package.13 Analytical transmission electron microscopy (ATEM) The as-synthesized samples of diamond-like BCN phases were suciently brittle to be crushed between two glass slides.

The powdered samples were dispersed in a droplet of ethanol and then loaded on copper grids coated with a holey carbon lm. For comparison, we also prepared samples of starting graphite-like material, diamond and cBN in a similar way. The samples were studied using a PHILIPS CM20 eld emission gun transmission electron microscope (FEG-TEM) operating at 200 kV. The microstructure of the samples was characterized by bright-eld (BF) and high-resolution transmission electron microscopy (HRTEM) as well as by selected area electron diraction (SAED) (Figs. 1 and 2). To obtain interplanar spacings of the cubic BCN compounds, SAED ring patterns were scanned and quantitatively evaluated using the Process Diraction program.14 The three strongest diraction rings 111, 220, and 311 were then used for the renement of the lattice constant a (Fig. 3). The camera constant was calibrated with diamond and cBN standards, operating the TEM under the same diraction conditions as employed for BCN compounds. Errors in the lattice constant a are estimated to be 0.01 A. The electron energy loss spectra (EELS) of the B K, C K, and N K edges were detected with the GATAN parallel electron energy-loss spectrometer (PEELS 666). Measurements were performed in diraction mode at a camera length of 210 mm, using a 2 mm entrance aperture. The energy resolution dened as full width at half maximum height of the zero-loss peak was 0.8 eV. EELS measurements were performed with two energy dispersions: 0.1 eV per channel and

Fig. 1 Bright-eld TEM images of (a) graphite-like BC2N precursor and nanocrystalline diamond-like BCN phases synthesized in (b) multianvil, (c) diamond-anvil cell and (d) shockcompression experiments.

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Fig. 2 Selected area electron diraction patterns of (a) graphite-like BC2N precursor and nanocrystalline diamond-like BCN phases synthesized in (b) multianvil, (c) diamond-anvil and (d) shockcompression experiments.

Fig. 4 Electron energy-loss spectra of various diamond-like BCN phases and graphite-like BC2N precursor showing the B K, C K, and N K ionization edges. The spectra were acquired with an energy dispersion of 0.3 eV per channel. The background was, in part, removed by tting an inverse power law function to the B K pre-edge region. MA refers to multi-anvil experiments, DAC to diamond anvil cell and SC to shockcompression experiments.

0.3 eV per channel. The latter energy dispersion allowed us to simultaneously detect all three edges and to determine the chemical composition of compounds according to the equation CA sB b; DEIA b; DE CB sA b; DEIB b; DE where CA and CB are the atomic concentrations of the elements A and B.15 s and I are the partial ionization cross sections and intensities of the K ionization edges, respectively. They were determined for a collection semi-angle b 2.7 mrad and an energy window DE 50 eV. The partial ionization cross sections were experimentally calibrated using cBN and gBC2N as standards. Especially in the case of light elements, the use of standards for quantifying compositions is superior to the theoretical calculation of partial ionization cross sections. From charge balance considerations the number of boron and nitrogen atoms should be identical in the

BCN compounds, which provides a means to estimate the errors in analyses. The data in Table 1 suggest that the relative errors in boron and nitrogen concentrations are up to 10%. The 0.3 eV per channel spectra were also used to determine the exact energy loss positions of B K and N K edges for BC N phases synthesized (Fig. 4). The energy position of the s* peak maximum in the C K spectra was assumed to be at 291.7 eV. The exact energy dispersion of the spectrometer was determined using the calibration routine in the GATAN EL/P software. The energy dispersion of 0.1 eV per channel was selected to reveal, with good energy resolution, the energy-loss nearedge structure (ELNES) of the B K, C K, and N K edges (Figs. 57). In each series of measurements, six ELNES spectra were acquired and summed. Furthermore, data reduction involved the correction for dark current and channel-tochannel gain variation, the subtraction of an inverse power law background, and the removal of plural scattering contributions by the Fourier-ratio technique.15 For comparison, the ELNES spectra of all samples were normalized to unity.

Results
Graphite-like BC2N precursor The X-ray diraction pattern of the precursor material, graphite-like (BN)0.48C0.52 , exhibits diuse 002, 100, 101 and 004 lines, which is indicative of the very disordered, poorly crystalline state of the material. The lattice parameter a 2.48(2) A is intermediate between the corresponding values for graphite (2.46 A) and BN (2.51 A) while the inter is much greater than those in layer spacing d002 3.64(2) A turbostratic carbon (3.44 A) and graphite-like BN (3.43 A).9 At the TEM scale, the phase shows a turbostratic structure (Fig. 1a). It is impossible to dene grains or grain boundaries because the material is almost amorphous. This is also evident from the selected area electron diraction pattern (Fig. 2a), which displays broad diuse rings similar to those of turbostratic graphite. The C K ELNES spectrum of graphite-like BC2N is also in line with this interpretation. It contains the Phys. Chem. Chem. Phys., 2002, 4, 51835188 5185

Fig. 3 Variation in lattice parameter a of synthesized diamond-like BCN phases (cBCN) as a function of the carbon concentration. Lattice parameters of the end-members of the BNC solid solution, diamond and cBN, are shown for comparison. Circles represent electron diraction data, the triangle represents the X-ray diraction data.

Fig. 5 B K ELNES spectra of various diamond-like BCN phases in comparison with the spectra of cubic BN and graphite-like BC2N precursor.

Fig. 7 N K ELNES spectra of various diamond-like BCN phases in comparison with the spectra of cubic BN and graphite-like BC2N precursor.

p* peak at 285 eV followed by a relatively featureless, broad s* peak (Fig. 6). These spectral characteristics are similar to those for amorphous carbon but quite dierent to those of well-crystallized graphite, displaying a complex ne structure with a number of sharp peaks (Fig. 6). Diamond-like BC3N synthesized in a multianvil press According to the quantication of the EELS spectra, the stoichiometries of the two BCN samples synthesized in dierent

Fig. 6 C K ELNES spectra of various diamond-like BCN phases and the graphite-like BC2N precursor in comparison to the spectra of diamond, graphite and amorphous carbon.

multianvil (MA) experiments are (BN)0.43C0.57 and (BN)0.41C0.59 (Table 1, Fig. 4). Considering the errors in the determination of the light elements and the similar synthesis conditions, both samples may have an almost identical composition, with an average stoichiometry (BN)0.42C0.58 (or simpler, approximately BC3N). They seem hence to contain 6% less BN component than the graphite-like BC2N precursor material. The X-ray diraction pattern of one of the BC3N samples exhibits only 111, 220, and 311 lines of the cubic lattice (Fd3m space group) with the lattice parameter of 3.611(6) A, ) and close to which is larger than that of diamond (3.5667 A that of cBN (3.6158 A) (JCPDS NN. 6-0675 and 35-1365, respectively). The absence of the 200 line indicates that the atomic scattering factors of the two zinc blende-type fcc sublattices in cBC3N are equal, which is possible only if B, C and N atoms are uniformly distributed over both sublattices. According to the TEM observations, the produced cubic phases occur as nanocrystalline aggregates with clearly visible but very small (average size: 2030 nm) grains (Fig. 1b). The largest grains show regular crystal shapes with cubic forms (octahedra and cubes), while smaller grains appear to be round. In line with X-ray results, SAED patterns are fully compatible with the diamond structure and exhibit sharp rings with numerous discrete spots corresponding to the 111, 220 and 311 reections of the cubic phase (Fig. 2b). The lattice parameters a of the two samples, derived from electron dirac tion data, are 3.58(1) A and 3.60(1) A (Table 1). These lattice parameters are intermediate between those of diamond (3.5667 A; JCPDS NN. 6-0675) and cBN (3.6158 A, space group: F43m; JCPDS NN. 35-1365), as expected from ideal mixing between these two endmembers of the BNC solid solution (Fig. 3). Superstructures could not be observed, pointing also to a statistical uniform distribution of B, C, and N atoms in the crystal lattice. B K, C K, and N K ELNES spectra of the two cBC3N samples resemble very much those of diamond and cBN (Figs. 57). The p* peak is almost completely absent and the ne structure of the ELNES spectra ts very well to a phase with almost pure sp3 type atomic bonding and tetrahedral coordination of B, C, and N atoms. The only clear dierence

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between the ELNES spectra of diamond and cBN is the marginal broadening of peaks.

Diamond-like BC8N phase synthesized in a DAC In situ X-ray studies of the graphite-like BC2N in the 2532 GPa pressure range at temperatures above 2900 K using laser-heated DAC show complex X-ray diagrams with overlapping peaks of cubic phases. The data suggest that the precursor material has decomposed into diamond, cubic boron nitride and another cubic phase. To further inspect this decomposition reaction and to characterize the new phase assemblage we used the TEM. The DAC sample is composed of separate, about 1 mm large polycrystalline aggregates of cBN, diamond, and a cubic BCN compound, which is distinctly depleted in the BN component (Fig. 4). The evaluation of the EELS spectrum yields a composition of (BN)0.21C0.79 , i.e. approximately BC8N (Table 1). This indicates a decomposition reaction of the gBC2N precursor into the assemblage cBN + C (diamond) + cBC8N. The grain size of the idiomorphic BC8N crystallites within the aggregates is of the order of 2030 nm (Fig. 1c). The corresponding SAED pattern ts to the diamond structure and shows sharp 111, 220, and 311 diraction rings with discrete spots (Fig. 2c). The lattice constant a 3.57(1) A is in agreement with the linear variation of the a parameter as a function of carbon content (Fig. 3). The B K, C K, and N K ELNES spectra are fully compatible with a diamond-structured material but are slightly less sharp than those of diamond and cBN (Figs. 57). Diamond-like BC2N synthesized by shock compression According to the EELS results (Table 1, Fig. 4), the stoichiometry of the sample recovered from the shock compression (SC) experiment is (BN)0.53C0.47 (or simpler, approximately BC2N). The BN content is slightly higher than that of the graphite-like BC2N starting material. It is unlikely that this small dierence is due to a preferential loss of carbon but it possibly results from heterogeneities in the precursor material. The X-ray diraction pattern of the sample exhibits broad 111, 220 and 311 lines, while the 200 line is missing. B, C and N atoms are hence statistically distributed over the crystal lattice. A prole analysis of the 220 and 311 lines did not reveal overlapping or asymmetric peaks. It follows thus that the experimentally observed diraction patterns are solely attributable to a diamond-like BNC uniform solid solution, and not to a mechanical mixture of diamond and cBN. The lattice parameter of c(BN)0.53C0.47 has been found to be 3.593(4) A and is in a good agreement with the corresponding value (3.591 A) that should be expected from ideal mixing between diamond and cBN (Fig. 3). Under TEM, the sample is polycrystalline with an average grain size of about 5 nm (Fig. 1d). In contrast to the BCN compounds synthesized at static pressures, the grains of shock-synthesized BC2N are irregularly shaped and are poorly crystallized, as is obvious from the corresponding electron diffraction pattern displaying broadened lines with very few discrete spots (Fig. 2d). Similarly broad lines are also observed for the graphite-like precursor (Fig. 2a). Besides the line broadening, the SAED pattern of shock-synthesized cubic BC2N is fully consistent with the diamond structure. No extra peaks or streaks appeared that would indicate the presence of a superstructure with an ordered stacking sequence. Overall, the B K, C K, and N K ELNES spectra are similar to those of diamond and cBN but the ne structure of the edges is distinctly less sharp (Figs. 57). The p* peak is clearly visible in the C K spectrum but seems to be absent in the B K and N K spectra. Among all synthesized cubic BCN compounds, the

Fig. 8 Electron energy-loss spectra of shock-synthesized BC2N before and after electron irradiation. The appearance of p* peaks at all three edges reveals the breakdown of the cubic structure to an amorphous state with sp2 hybridization.

shock-produced sample is also the most beam-sensitive. After about 1 min of electron irradiation the EELS spectrum of shock-synthesized BC2N completely changed into a spectrum, which resembles that of the precursor material (Fig. 8). The three B K, C K, and N K edges contain a strong p* pre-peak and the following edge is featureless, indicating the structural breakdown of the material under the beam.

Discussion
BN solubility in the diamond structure Our EELS data show that almost all synthesized diamond-like BCN phases have changed their compositions in comparison to the graphite-like BC2N precursor (Table 1, Fig. 4). The only exception is the shock-synthesized BC2N sample, which due to the short duration of the shock pulse (only about 1 ms) could not change composition. Additionally, the shock-synthesized cubic BC2N apparently inherited some microstructural properties of the graphite-like BC2N precursor, such as the poor crystallinity and irregular shape of grains. For the other samples, there is a clear tendency that higher temperatures and/or longer annealing result in a lower BN concentration in the diamond structure. This eect is most obvious for the DACsynthesized sample, which contains separate aggregates of cBN and diamond that are associated with a new cubic B CN phase with the approximate stoichiometry BC8N. This observation demonstrates that cBN and diamond have segregated out of the BC2N precursor, forming consequently the depleted cBC8N phase. At the synthesis conditions, the diamond-structured phases are obviously supersaturated in BN and therefore tend to decompose. Equilibrium was not reached in the experiments, possibly because of the low diusivity of B and N in the diamond structure. An additional kinetic barrier could be that B and N can only be expelled from the diamond structure by a coupled diusion mechanism, fullling the requirement of the charge balance. For a better understanding of the diusion mechanism, it is however mandatory to measure concentration proles across cubic BCN grains, as has been successfully demonstrated for graphitic BC2N nanotubes.16,17 Based on our observations, one can expect that, under equilibrium conditions, the BN solubility in diamond is quite limited. These conclusions are strengthened by the observation reported in ref. 18, that cubic BCN phases could not be synthesized from very ne-grained mechanical mixtures of hBN and graphite. In order to grow cubic ternary phases with a high BN Phys. Chem. Chem. Phys., 2002, 4, 51835188 5187

concentration, hence, it is necessary to use precursor materials that are perfect chemical BCN mixtures with large grains. Short-range structure of cubic BCN compounds X-ray and electron diraction data show that the synthesized BCN phases possess the diamond structure with space group Fd3m (Fig. 2). The absence of extra reections, such as the 200 line, indicates that superstructures are not formed under synthesis conditions. The lattice parameter a shows a linear dependence on composition (Fig. 3), which is characteristic for ideal mixing between diamond and cBN, the end-members of the BNC solid solution. These results reveal that the BN component is homogeneously dissolved in the diamond crystal lattice. Further hints as to the incorporation and short-range structural eect of BN in diamond-structured phases is provided by the ELNES spectra, which are a ngerprint of the local environment of the excited atom. For a better understanding of the spectral characteristics, we compare and discuss here the ELNES spectra of synthesized diamond-like BCN phases with those of diamond, cBN, and graphite-like BC2N precursor (Figs. 57). In terms of edge shape and energy positions, the B K, C K and N K ELNES spectra of the diamond-like BCN phases are similar to those of cBN and diamond (Figs. 57). The positions of the onset peaks in the B K, C K, and N K spectra of the cubic BCN phases are at 197.7, 291.7, and 406.3 eV, respectively. These energy positions signicantly dier from those reported in ref. 19 for cubic BC2N. The onset peaks in the B K and N K spectra of cBN seem to be only marginally shifted to 197.4 and 406.6 eV, respectively (Figs. 5 and 7). These values are in reasonable agreement with the data reported in ref. 2022 for cBN but dier by more than 2 eV from the measurements given in ref. 23. A detailed comparison between the dierent cubic phases of the BCN concentration triangle reveals, however, a clear difference in the sharpness of the ELNES spectra. Diamond and cBN clearly yield the best-resolved ELNES spectra with sharp peaks. The ELNES spectra of all cubic BCN phases are less sharp, particularly at the edge onset. The shock-synthesized, most beam-sensitive cBC2N phase shows the strongest broadening of the ELNES signals. Additionally, one notes the presence of a pre-peak in the C K spectra of cubic BCN compounds at about 4 eV before the edge onset, i.e. at the position of the p* peak for the graphite-like BC2N. One could argue that this pre-peak is due to contamination under the electron beam but then we would expect to detect this peak for diamond and cBN, as well. The p* pre-peak at the C K edge seems rather to be related to the BN content in the cubic BCN phases, since its intensity increases with BN concentration (Fig. 6). Recently, the spectral features of the B K and N K ELNES spectra were related to structural elements in cubic and hexagonal (wurtzite-structured) BN, using rst-principles MO calculations.24 According to these calculations, the onset peak in the B K and N K spectra is strongly dominated by the core hole eect and may provide information on the regularity of the tetrahedra, whereas peaks at higher energy losses provide information on the tetrahedral stacking, i.e. on the secondnearest neighbours. The broadening of the onset peaks in the B K, C K and N K ELNES spectra may therefore indicate that the tetrahedra in the cubic BCN phases are irregularly and variably distorted and that this short-range disorder increases with BN content. Regarding the weak p* signal in the pre-edge region of the C K ELNES spectra, it has been previously demonstrated that this peak may result from dislocations or other types of defects.15,2527 We could, hence, interpret the weak p* peaks in our spectra of cubic BCN as the result of transitions to localized defect states. The fact that only the C K spectrum of BCN compounds contains this pre-edge signal may 5188 Phys. Chem. Chem. Phys., 2002, 4, 51835188

indicate that the defects are located at carbon sites in the diamond structure. Since dislocations are absent in all our samples, we assume that point defects or surface defects could be responsible for such localized defect states. Indeed, the shock-synthesized cBC2N phase, which is the most imperfect and disordered sample with large surface area, shows the strongest pre-edge signal.

Acknowledgements
The authors thank D. Andrault, D. Frost, M. Mezouar, T. Peun and D.C. Rubie for their assistance with synthesizing samples and A.V. Kurdyumov for helpful discussions. Multianvil synthesis was performed at the Bayerisches Geoinstitut under the EU IHP Access to Research Infrastructures Program (Contract No. HPRI-1999-CT-00004 to D.C. Rubie). The DAC experiments were carried out during beamtime allocated to proposals HS-918 and HS-1693 at ID30, European Synchrotron Radiation Facility. Shockcompression experiments were supported by the Dynamit Nobel GmbH.

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