Papers by Igor Kupriyanov
Micromachines, 2021
Gas-phase etching and optical lithography were employed for the fabrication of a silicon nanoribb... more Gas-phase etching and optical lithography were employed for the fabrication of a silicon nanoribbon chip (Si-NR chip). The quality of the so-fabricated silicon nanoribbons (Si-NRs) was monitored by optical Raman scattering spectroscopy. It was demonstrated that the structures of the Si-NRs were virtually defect-free, meaning they could be used for highly sensitive detection of biological macromolecules. The Si-NR chips were then used for the highly sensitive nanoelectronics detection of DNA oligonucleotides (oDNAs), which represent synthetic analogs of 106a-5p microRNA (miR-106a-5p), associated with the development of autism spectrum disorders in children. The specificity of the analysis was attained by the sensitization of the Si-NR chip sur-face by covalent immobilization of oDNA probes, whose nucleotide sequence was complementary to the known sequence of miR-106a-5p. The use of the Si-NR chip was demonstrated to al-low for the rapid label-free real-time detection of oDNA at ultra...
CrystEngComm, 2020
Sulfur additives inhibit diamond crystallization in the Fe–Ni–C system at 6 GPa and 1400 °C and a... more Sulfur additives inhibit diamond crystallization in the Fe–Ni–C system at 6 GPa and 1400 °C and affect the diamond crystal morphology and nitrogen impurity content.
Science Advances, 2021
Localized electric fields induce diamond crystallization from carbonates under P - T conditions o... more Localized electric fields induce diamond crystallization from carbonates under P - T conditions of Earth’s mantle.
Carbon, 2018
Abstract Development of new routes for fabrication of diamond containing color centers with speci... more Abstract Development of new routes for fabrication of diamond containing color centers with specific optical and magnetic properties is important for its employment in many innovative applications such as the emerging quantum technologies. Here we report a systematic study on the high-pressure synthesis of diamond from various tin-containing systems aimed at establishing growth conditions favorable for the incorporation of Sn atoms in crystallized diamonds with the formation of the tin-vacancy (Sn V) color centers. Synthesis experiments are performed at 6.3–7.5 GPa and 1400–1900 °C using solvent-catalysts of three different types: Fe Sn Al, Sn-(Ti, Al, Zr) and Sn Mg. We established the main features of diamond crystallization from these catalysts and determined photoluminescence characteristics of the synthesized diamonds. It is found that over the range of the P-T conditions and catalyst compositions employed in the study, the Sn Mg C system is a most effective medium for growing Sn-doped single crystal diamond. We show that with the approach developed in the study it is possible to fabricate diamond single crystals with sizes from ∼50 μm to ∼1 mm containing high-quality Sn V color centers with narrow zero-phonon lines.
Crystals, 2017
Crystallization of diamond in the Mg-Si-C system has been studied at 7.5 GPa and 1800 • C with th... more Crystallization of diamond in the Mg-Si-C system has been studied at 7.5 GPa and 1800 • C with the Mg-Si compositions spanning the range from Mg-C to Si-C end-systems. It is found that as Si content of the system increases from 0 to 2 wt %, the degree of the graphite-to-diamond conversion increases from about 50 to 100% and remains at about this level up to 20 wt % Si. A further increase in Si content of the system leads to a decrease in the graphite-to-diamond conversion degree down to complete termination of diamond synthesis at Si content >50 wt %. Depending on the Si content crystallization of diamond, joint crystallization of diamond and silicon carbide and crystallization of silicon carbide only are found to take place. The cubic growth of diamond, typical of the Mg-C system, transforms to the cube-octahedron upon adding 1 wt % Si and then to the octahedron at a Si content of 2 wt % and higher. The crystallized diamonds are studied by a suite of optical spectroscopy techniques and the major characteristics of their defect-and-impurity structure are revealed. The correlations between the Si content of the Mg-Si-C system and the properties of the produced diamond crystals are established.
Crystal Growth & Design, 2016
Here we report on successful synthesis of Ge-doped single crystal diamond at high-pressure high-t... more Here we report on successful synthesis of Ge-doped single crystal diamond at high-pressure high-temperature (HPHT) conditions of 7.0 GPa and 1500–1900 °C from an Mg–Ge–C system. The systematic study of diamond crystallization processes reveals that addition of Ge to the Mg–C system suppresses the intensity of diamond spontaneous nucleation enabling synthesis of relatively large (2–3 mm) diamond crystals via seeded growth. Temperature is found to be a key factor controlling diamond crystallization mechanisms, morphological characteristics, and optical properties of the crystals. It is established that the diamond growth rate depends almost exponentially on the temperature increasing from 3.3 μm/h at 1500 °C to 4.2 mm/h at 1900 °C. Spectroscopic characterization of the synthesized diamonds reveals the abundance of the 2.06 eV Ge–V centers in the photoluminescence spectra confirming successful doping of the diamonds with germanium. The feasibility of the Mg–Ge–C system for growing bulk low-strain diamond dop...
physica status solidi (a), 2016
In this work, high pressure high temperature (HPHT) diamonds synthesized in the Mg-C system with ... more In this work, high pressure high temperature (HPHT) diamonds synthesized in the Mg-C system with germanium, silicon and boron additives were studied. In the photoluminescence spectra of the samples doped with Ge, an intense system 602 nm attributed to germanium-vacancy defects was detected. In the electron paramagnetic resonance (EPR) spectra of these samples, a new paramagnetic center with S ¼ 1 was detected along with substitutional nitrogen P1 and silicon-vacancy KUL1 (SiV 0) centers. The angular dependence investigation of the new spectrum allowed us to establish its spin Hamiltonian parameters: g || ¼ 2.0025, g ? ¼ 2.0027, D ¼ 80.3 mT, E ¼ 0. The center was determined to have the symmetry axis parallel to h111i. Hyperfine structure (HFS) of one 73 Ge atom (I ¼ 9/2) was observed for the new spectrum. The novel paramagnetic center was proposed to be the neutral germanium split-vacancy defect. EPR and luminescence studies of diamonds doped with Si and B revealed a new paramagnetic center that can be associated with the sharp luminescence system 720 nm. An analysis of the angular dependence of the EPR spectrum showed that it had electronic spin S ¼ 1/2 and anisotropic g-factor: g 1 ¼ 2.0033, g 2 ¼ 2.0004, and g 3 ¼ 2.0024. Based on the principal values and directions of the g-tensor the detected center was suggested to have the structure of silicon and boron atoms in the nearest carbon positions.
Diamond and Related Materials, 2015
Diamond crystallization from the tin-carbon system has been studied at 7 GPa and temperatures ran... more Diamond crystallization from the tin-carbon system has been studied at 7 GPa and temperatures ranging from 1600 to 1900°C with reaction times from 1 to 20 h. Both diamond growth on the seed crystals and diamond spontaneous nucleation were established, providing evidence for the catalytic ability of tin. A distinctive feature of the Sn-C system is the existence of a significant induction period preceding diamond spontaneous nucleation. Temperature and kinetics are found to be the main factors governing diamond crystallization process. The minimum parameters of diamond spontaneous nucleation are determined to be 7 GPa, 1700°C and 20 h. The stable form of diamond growth is octahedron and it does not depend on temperature. Synthesized diamonds contain high concentrations of nitrogen impurities up to about 1600 ppm.
Scientific Reports, 2015
Diamond attracts considerable attention as a versatile and technologically useful material. For m... more Diamond attracts considerable attention as a versatile and technologically useful material. For many demanding applications, such as recently emerged quantum optics and sensing, it is important to develop new routes for fabrication of diamond containing defects with specific optical, electronic and magnetic properties. Here we report on successful synthesis of diamond from a germanium-carbon system at conditions of 7 GPa and 1,500–1,800 °C. Both spontaneously nucleated diamond crystals and diamond growth layers on seeds were produced in experiments with reaction time up to 60 h. We found that diamonds synthesized in the Ge-C system contain a new optical centre with a ZPL system at 2.059 eV, which is assigned to germanium impurities. Photoluminescence from this centre is dominated by zero-phonon optical transitions even at room temperature. Our results have widened the family of non-metallic elemental catalysts for diamond synthesis and demonstrated the creation of germanium-related ...
American Mineralogist, 2014
The phase relations in the Na 2 CO 3-(Fe 0.87 Mn 0.06 Mg 0.07)CO 3 system have been studied in Ka... more The phase relations in the Na 2 CO 3-(Fe 0.87 Mn 0.06 Mg 0.07)CO 3 system have been studied in Kawai-type multianvil experiments using graphite capsules at 6.0 GPa and 900-1400 °C. Subsolidus assemblages comprise the stability fields of Na 2 CO 3 + Na 2 Fe(CO 3) 2 and Na 2 Fe(CO 3) 2 + siderite with the transition boundary at X(Na 2 CO 3) = 50 mol%. Intermediate Na 2 Fe(CO 3) 2 compound has rhombohedral 3 R eitelite structure with cell parameters a = 4.9712(16) Å, c = 16.569(4) Å, V = 354.61(22). The Na 2 CO 3-Na 2 Fe(CO 3) 2 eutectic is established at 1000 ºC and 66 mol% Na 2 CO 3. Na 2 Fe(CO 3) 2 disappears between 1000 and 1100 ºC via incongruent melting to siderite This is a preprint, the final version is subject to change, of the American Mineralogist (MSA) Cite as Authors (Year) Title. American Mineralogist, in press. (DOI will not work until issue is live.
physica status solidi (a), 2015
physica status solidi (a), 2014
An electron paramagnetic resonance (EPR) study of synthetic diamond crystals grown at HTHP condit... more An electron paramagnetic resonance (EPR) study of synthetic diamond crystals grown at HTHP conditions in the carbonate medium Na 2 CO 3-CO 2-H 2 O-C has revealed a hydrogencontaining center (VOH) along with centers OX1, OX2, and OX3 tentatively associated with oxygen. In the X-band EPR spectra, the forbidden transitions of the center are superimposed on the allowed HFS lines of one hydrogen atom. We have succeeded in analysis of the allowed transitions in Q-band experiments. On the basis of the obtained experimental data a hypothetical model of the center has been proposed as a vacancy-oxygen complex with incorporated hydrogen atom. The occurrence of hydrogen in the studied diamond crystals is supported by the presence of C-H vibrations in the IR spectra in the range of 3000 cm À1 .
physica status solidi (a), 2013
ABSTRACT
physica status solidi (a), 2013
ABSTRACT
Handbook of Crystal Growth, 2015
Abstract In this chapter we have presented a review of the state-of-the-art of diamond crystal gr... more Abstract In this chapter we have presented a review of the state-of-the-art of diamond crystal growth using high pressure high temperature (HPHT) and chemical vapor deposition (CVD) approaches. We considered the main methods, techniques, and equipment used for single crystal diamond growth. Special attention is given to discussing the effects of growth conditions on the growth and properties of diamond. Current achievements in HPHT and CVD growth of single crystal diamond and its applications are considered.
Journal of Crystal Growth, 2014
The real structure of the {111} sectors of large single synthetic diamond crystals with different... more The real structure of the {111} sectors of large single synthetic diamond crystals with different nitrogen contents has been studied by the selective etching method: (1) nitrogen-gettered diamonds with nitrogen impurity content at a level of 1-2 ppm, (2) diamond crystals grown without additives with nitrogen impurity of 180-220 ppm and (3) diamonds nitrogen alloyed during growth up to the concentrations of 550-600 ppm. All diamond crystals have been grown by the temperature gradient method using the high pressure apparatus of "split-sphere" type (BARS) at T¼1350 1C, P¼5.7 GPa and (100) seed crystal. It is found that the density of dislocations increases from 85 cm À 2 to 4.0 Â 10 3 cm À 2 and the total length of planar defects increases from 30 to 300 μm/cm 2 as the nitrogen content in the crystals increases up to 600 ppm. It is shown that partial dislocations are the dominant dislocations (60-90%) in all the crystals studied. A proportion of perfect dislocations increases as the nitrogen content in crystals, and correspondingly, the dislocation density increase. Possible causes for the increase of the extended defects density in the synthetic diamond crystals with the nitrogen impurity concentration rise are discussed.
Journal of Crystal Growth, 2011
Octahedral diamond crystals grown by the temperature gradient method at 1550 1C using a BARS appa... more Octahedral diamond crystals grown by the temperature gradient method at 1550 1C using a BARS apparatus have been studied. Dislocations and planar defects in diamond crystals have been found and characterized by selective etching and X-ray diffraction topography. It is found that the diamond crystals contained not more than four bunches of extended defects. Large planar defects and narrow bunches of straight /1 1 1S dislocations extend from the seed crystal. /1 1 1S dislocations initiate stacking faults and partial dislocations in the /1 1 2S direction. These defects also give rise to /2 2 1S dislocations. Partial dislocations are dominant. Screw and then edge and mixed dislocations appear as the densities of linear and planar defects increase in the bunch. Combined cathodo-and photoluminescence topographic, X-ray topographic and selective etching studies of {1 1 1} faces showed, that single /1 1 1S dislocations are the sources of large low-elevation hillocks, which appeared during crystal growth. It is concluded that diamond crystal growth at the specified average rates of 39-45 mm/h is a phenomenon involving the simultaneous participation of dislocations and two-dimensional nucleation as sources of growth steps. The studies have shown that dislocation-free regions in the octahedral diamond crystals weighing 3 carats occupy about 58 mm 3 , and some crystals have completely dislocation-free {1 1 1} growth sectors.
Geochimica et Cosmochimica Acta, 2010
High pressure experiments have been performed in the systems Mg 2 SiO 4-CO -H and Mg 2 SiO 4-K 2 ... more High pressure experiments have been performed in the systems Mg 2 SiO 4-CO -H and Mg 2 SiO 4-K 2 CO 3-C at 6.3 GPa and 1200 to 1600°C using a split-sphere multi-anvil apparatus. In the Mg 2 SiO 4-CO -H system the composition of fluid was modeled by adding different amounts of water and stearic acid. The fO 2 was controlled by the Mo-MoO 2 or Fe-FeO oxygen buffers. Several experiments in the Mg 2 SiO 4-CO -H system and all experiments in the Mg 2 SiO 4-K 2 CO 3-C system have been conducted without buffering the fO 2. Forsterite in the system Mg 2 SiO 4-K 2 CO 3-C does not reveal OH absorption bands in the IR spectra, while forsterite coexisting with carbon-bearing fluid and silicate melt at logfO 2 from FMQ-2 to FMQ-5 (from 2 to 5 log units below fayalite-magnetite-quartz oxygen buffer) contains 800-1850 wt. ppm H 2 O. The maximum concentrations were detected at 1400°C and FMQ-3.5. We observed an increase in the solidus temperature in the system Mg 2 SiO 4-CO -H from 1200 to above 1600°C with log fO 2 decreasing from FMQ-2 to FMQ-5. The increase of the solidus temperature and the broadening of the stability field of the H 2 O-H 2-CH 4 subsolidus fluid phase at 1400-1600°C explain the high H 2 O storage capacity of forsterite relative to that crystallized from carbon-free, oxidized, hydrous, silicic melt. At temperatures above 1400°C liquidus forsterite precipitated along with diamond from oxidized (FMQ-1) carbonate-silicate melt and from silicate melt dissolving the moderately reduced CO -H fluid (from FMQ-2 to FMQ-3.5). Formation of diamond was not detected under ultra-reduced conditions (FMQ-5) at 1200-1600°C. Olivine co-precipitating with diamond from dry carbonate-silicate or hydrous-silicic fluid/melt can provide information on the H 2 O contents and speciation of the diamond-forming media in the mantle. The conditions for minimum post-crystallization alteration of olivine and its hydrogen content are discussed.
European Journal of Mineralogy, 2012
ABSTRACT Comprehensive studies of diamond crystals with a low nitrogen concentration from the pla... more ABSTRACT Comprehensive studies of diamond crystals with a low nitrogen concentration from the placer deposits and kimberlite pipes of Yakutia have facilitated the detection of three titanium-nitrogen-related centers: OKI/S1, N3/440.3 nm and NU1/485 nm in the EPR and photoluminescence spectra. Additional proof of titanium presence in the structure of EPR N3 center was obtained from the hyperfine structure of titanium magnetic isotopes Ti-47 and Ti-49. Titanium-nitrogen-related centers in the neighboring substitutional sites (N3/440.3 nm) and in the structure of the < 100 > interstitial (NU1/485 nm) are not found in cubic habit crystals, which are characterized by the presence of the OK1/S1 center with a double semi-vacancy structure. All three types of nitrogen-titanium-related centers are present in cuboctahedral habit diamonds. It is assumed that these habit-specific distributions of defects in diamond are a result of the peculiarities of incorporating nitrogen and titanium impurities into the different growth sector of crystals and aggregation thereof at high pressure and temperature.
Earth and Planetary Science Letters, 2013
Partitioning of H 2 O between olivine and carbonate-silicate melts has been studied at 6.3 GPa an... more Partitioning of H 2 O between olivine and carbonate-silicate melts has been studied at 6.3 GPa and 1400 • C using a split-sphere multianvil apparatus. Olivine was synthesized in equilibrium with hydrous silicate and hydrous carbonate-silicate±chloride melts saturated with respect to one of Opx, Grt, Ms or a harzburgitic (Ol+Opx+Grt) residue and had CO 2 /(CO 2 +SiO 2) molar ratios from 0 to 0.8. The concentration of H 2 O in olivine was determined using FTIR spectroscopy. We found that depending on the melt carbonation and saturation in equilibrium silicate phases the H 2 O content in olivine varied from 100 to 1500 ppm. The obtained results and data reported in Sokol et al. (2013) indicate that H 2 O content in olivine becomes approximately two times lower as CO 2 /(CO 2 +SiO 2) molar ratios in the equilibrium melt increases from 0 to 0.4-0.8 and the crystallization media transform from hydrous silicate to hydrous carbonate-silicate (kimberlite like) melt. The estimated water partitioning between carbonate-silicate melt and nominally anhydrous mantle minerals indicates that carbonatitic melt can effectively extract water once it invades H 2 O-poore the peridotite. We suggest that extraction of H 2 O owing to the freezing point depression may provide the necessary melting degree of metasomatized peridotite source and formation of kimberlitic magma.
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Papers by Igor Kupriyanov