A series of diamond crystals doped with hydrogen is successfully synthesized using LiH as the hydrogen source in a catalyst-carbon system at a pressure of 6.0 GPa and temperature ranging from 1255 C to 1350 C.It is sh...A series of diamond crystals doped with hydrogen is successfully synthesized using LiH as the hydrogen source in a catalyst-carbon system at a pressure of 6.0 GPa and temperature ranging from 1255 C to 1350 C.It is shown that the high temperature plays a key role in the incorporation of hydrogen atoms during diamond crystallization.Fourier transform infrared micro-spectroscopy reveals that most of the hydrogen atoms in the synthesized diamond are incorporated into the crystal structure as sp 3-CH 2-symmetric(2850 cm-1) and sp 3 CH 2-antisymmetric vibrations(2920 cm-1).The intensities of these peaks increase gradually with an increase in the content of the hydrogen source in the catalyst.The incorporation of hydrogen impurity leads to a significant shift towards higher frequencies of the Raman peak from 1332.06 cm-1 to 1333.05 cm-1 and gives rise to some compressive stress in the diamond crystal lattice.Furthermore,hydrogen to carbon bonds are evident in the annealed diamond,indicating that the bonds that remain throughout the annealing process and the vibration frequencies centred at 2850 and 2920 cm-1 have no observable shift.Therefore,we suggest that the sp 3 C-H bond is rather stable in diamond crystals.展开更多
The effect of the catalyst height on the morphology of diamond crystal is investigated by means of temperature gradient growth(TGG) under high pressure and high temperature(HPHT) conditions with using a Ni-based catal...The effect of the catalyst height on the morphology of diamond crystal is investigated by means of temperature gradient growth(TGG) under high pressure and high temperature(HPHT) conditions with using a Ni-based catalyst in this article. The experimental results show that the morphology of diamond changes from an octahedral shape to a cuboctahedral shape as the catalyst height rises. Moreover, the finite element method(FEM) is used to simulate the temperature field of the melted catalyst/solvent. The results show that the temperature at the location of the seed diamond continues to decrease with the increase of catalyst height, which is conducive to changing the morphology of diamond. This work provides a new way to change the diamond crystal morphology.展开更多
Additive Ba(N 3) 2 as a source of nitrogen is heavily doped into the graphite-Fe-based alloy system to grow nitrogendoped diamond crystals under a relatively high pressure (about 6.0 GPa) by employing the temperature ...Additive Ba(N 3) 2 as a source of nitrogen is heavily doped into the graphite-Fe-based alloy system to grow nitrogendoped diamond crystals under a relatively high pressure (about 6.0 GPa) by employing the temperature gradient method.Gem-grade diamond crystal with a size of around 5 mm and a nitrogen concentration of about 1173 ppm is successfully synthesised for the first time under high pressure and high temperature in a China-type cubic anvil highpressure apparatus.The growth habit of diamond crystal under the environment with high degree of nitrogen doping is investigated.It is found that the morphologies of heavily nitrogen-doped diamond crystals are all of octahedral shape dominated by {111} facets.The effects of temperature and duration on nitrogen concentration and form are explored by infrared absorption spectra.The results indicate that nitrogen impurity is present in diamond predominantly in the dispersed form accompanied by aggregated form,and the aggregated nitrogen concentration in diamond increases with temperature and duration.In addition,it is indicated that nitrogen donors are more easily incorporated into growing crystals at higher temperature.Strains in nitrogen-doped diamond crystal are characterized by micro-Raman spectroscopy.Measurement results demonstrate that the undoped diamond crystals exhibit the compressive stress,whereas diamond crystals heavily doped with the addition of Ba(N 3) 2 display the tensile stress.展开更多
We investigate the temperature field variation in the growth region of a diamond crystal in a sealed cell during the whole process of crystal growth by using the temperature gradient method (TGM) at high pressure and ...We investigate the temperature field variation in the growth region of a diamond crystal in a sealed cell during the whole process of crystal growth by using the temperature gradient method (TGM) at high pressure and high temperature (HPHT). We employ both the finite element method (FEM) and in situ experiments. Simulation results show that the temperature in the center area of the growth cell continues to decrease during the process of large diamond crystal growth. These results are in good agreement with our experimental data, which demonstrates that the finite element model can successfully predict the temperature field variations in the growth cell. The FEM simulation will be useful to grow larger high-quality diamond crystal by using the TGM. Furthermore, this method will be helpful in designing better cells and improving the growth process of gem-quality diamond crystal.展开更多
In this paper, we have reported an investigation on the evolution of nitrogen structures in diamond crystals which contain nitrogen donor atoms in the range of 1500 ppm–1600 ppm following an annealing treatment at a ...In this paper, we have reported an investigation on the evolution of nitrogen structures in diamond crystals which contain nitrogen donor atoms in the range of 1500 ppm–1600 ppm following an annealing treatment at a high pressure of about 6.5 GPa and high temperatures of 1920 K–2120 K. The annealing treatment was found to completely transform nitrogen atoms originally arranged in a single substitutional form(C-center), into a pair form(A-center), indicated from infrared(IR) spectra. The photoluminescence(PL) spectra revealed that a small fraction of nitrogen atoms remained in C-center form, while some nitrogen atoms in A-center form were further transformed into N3 and H3 center structures. In addition, PL spectra have revealed the existence of two newly observed nitrogen-related structures with zero phonon lines at 611 nm and 711 nm. All these findings above are very helpful in understanding the formation mechanism of natural diamond stones of the Ia-type, which contains nitrogen atoms in an aggregated form.展开更多
This paper reprots that with Ni-based catalyst/solvent and with a dopant of NaN 3,large green single crystal diamonds with perfect shape are successfully synthesized by temperature gradient method under high pressure ...This paper reprots that with Ni-based catalyst/solvent and with a dopant of NaN 3,large green single crystal diamonds with perfect shape are successfully synthesized by temperature gradient method under high pressure and high temperature in a China-type cubic anvil high-pressure apparatus (SPD-6×1200),and the highest nitrogen concentration reaches approximately 1214-1257 ppm calculated by infrared absorption spectra.The synthesis conditions are about 5.5 GPa and 1240-1300 C.The growth behaviour of diamond with high-nitrogen concentration is investigated in detail.The results show that,with increasing the content of NaN 3 added in synthesis system,the width of synthesis temperature region for growth high-quality diamonds becomes narrower,and the morphology of diamond crystal is changed from cube-octahedral to octahedral at same temperature and pressure,the crystal growth rate is slowed down,nevertheless,the nitrogen concentration doped in synthetic diamond increases.展开更多
Diamond is synthesized in an Fe-Ni-C system at high pressure and high temperature,the C sp^(3) content profile through different thicknesses of interface between diamond and the catalyst film is measured by using elec...Diamond is synthesized in an Fe-Ni-C system at high pressure and high temperature,the C sp^(3) content profile through different thicknesses of interface between diamond and the catalyst film is measured by using electron energy loss spectroscopy.It is found that the Csp^(3) content varies from 87.33% to 78.15% when the measured position is located at the inner face near the diamond and then changes to 6 μm further away.Transmission electron microscope examinations show that there are different phases in the interface,such as Fe3C,γ-(Fe,Ni),and graphite,but the graphite phase diminishes gradually towards the inner face of the interface.These results profoundly indicate that the carbon atoms,required for diamond growth,could only come from the carbon-rich phase,Fe3C,but not directly from the graphite.It is possible that carbon atoms from the graphite in the interface first react with Fe atoms to produce carbide Fe3 C during diamond synthesis at high pressure and high temperature.The Fe3 C finally decomposes into carbon atoms with the sp^(3) electron state at the interface to form the diamond.展开更多
In this paper,we report on the influence of annealing treatment on as-grown Ib-type diamond crystal under high pressure and high temperature in a china-type cubic anvil high-pressure apparatus.Experiments are carried ...In this paper,we report on the influence of annealing treatment on as-grown Ib-type diamond crystal under high pressure and high temperature in a china-type cubic anvil high-pressure apparatus.Experiments are carried out at a pressure of 7.0 GPa and temperatures ranging from 1700 C to 1900 C for 1 h.Annealing treatment of the diamond crystal shows that the aggregation rate constant of nitrogen atoms in the as-grown Ib-type diamond crystal strongly depends on diamond morphology and annealing temperature.The aggregation rate constant of nitrogen remarkably increases with the increase of annealing temperature and its value in octahedral diamond is much higher than that in cubic diamond annealed at the same temperature.The colour of octahedral diamond crystal is obviously reduced from yellow to nearly colorless after annealing treatment for 1 h at 1900 C,which is induced by nitrogen aggregation in a diamond lattice.The extent of nitrogen aggregation in an annealed diamond could approach approximately 98% indicated from the infrared absorption spectra.The micro-Raman spectrum reveals that the annealing treatment can improve the crystalline quality of Ib-type diamond characterized by a half width at full maximum at first order Raman peak,and therefore the annealed diamond crystals exhibit nearly the same properties as the natural IaA-type diamond stones of high quality in the Raman measurements.展开更多
Some dislocations, which are generated in the diamond single crystal during the diamond crystal growth from Fe-Ni-C system, may affect diamond crystal growth mode at high temperature-high pressure (HPHT). The concentr...Some dislocations, which are generated in the diamond single crystal during the diamond crystal growth from Fe-Ni-C system, may affect diamond crystal growth mode at high temperature-high pressure (HPHT). The concentric dislocation loops were successfully examined by Moire images. The surface morphologies of growing and as-grown diamond single crystals were observed by scanning electron microscopy (SEM). The concentric dislocation loops formation process and their effect on the diamond crystal growth mode were analyzed. It should be noted that whatever the nature of the dislocation is, should the Burgers vector of dislocation has a component at the direction normal to the growth interface, the dislocation will make the face parallel to the growth interface grow into spiral face. The presence of consecutive spiral steps on the diamond crystal surface also provides a direct evidence of the dislocation mechanism of diamond crystal growth.展开更多
In this paper,we explore diamond synthesis with a series of experiments using an Fe-Ni catalyst and a P3N5 additive in the temperature range of 1250-1550 ℃ and the pressure range of 5.0-6.3 GPa.We also investigate th...In this paper,we explore diamond synthesis with a series of experiments using an Fe-Ni catalyst and a P3N5 additive in the temperature range of 1250-1550 ℃ and the pressure range of 5.0-6.3 GPa.We also investigate the influence of nitrogen on diamond crystallization.Our results show that the synthesis conditions(temperature and pressure) increase with the amount of P3N5 additive increasing.The nitrogen impurity can significantly influence the diamond morphology.The diamonds stably grow into strip and lamellar shapes in the nitrogen-rich environment.The Fourier-transform infrared spectrum shows that the nitrogen concentration increases rapidly with the content of P3N5 additive increasing.By spectrum analysis,we find that with the increase of the nitrogen concentration,the Ib-type nitrogen atoms can aggregate in the A-centre form.The highest A-centre nitrogen concentration is approximately 840 ppm.展开更多
In this paper,the diamond epitaxial growth mechanism has been studied in detail by employing several types of diamond as a seed in a catalyst-graphite system under high pressure and high temperature (HPHT) conditions....In this paper,the diamond epitaxial growth mechanism has been studied in detail by employing several types of diamond as a seed in a catalyst-graphite system under high pressure and high temperature (HPHT) conditions.We find that the diamond nucleation,growth rate,crystal orientation,and morphology are significantly influenced by the original seeds.The smooth surfaces of seeds are beneficial for the fabrication of high-quality diamond.Our results reveal that the diamond morphology is mainly determined by the original shape of seeds in the early growth stage,but it has an adjustment process during the growth and leads to well symmetry.Additionally,we have also established the growth model for the twinned diamond grown on several seeds,and proposed the possible growth processes by tracking the particular shapes of seeds before and after treatment under HPHT conditions.These results suggest that the shape-controlled synthesis of diamond with well morphology can be realized by employing certain suitable diamond seeds.This work is expected to play an important role in the preparation of trustworthy diamond-based electronic and photonic devices.展开更多
To elucidate the regulation mechanism of catalyst geometry structure to diamond growth,we establish three catalyst modes with different structures.The simulation results show that with the decrease of the protruding h...To elucidate the regulation mechanism of catalyst geometry structure to diamond growth,we establish three catalyst modes with different structures.The simulation results show that with the decrease of the protruding height of the catalyst,the low-temperature region gradually moves toward the center of the catalyst,which causes the distribution characteristics of the temperature and convection field in the catalyst to change.The temperature difference in vertical direction of the catalyst decreases gradually and increases in the horizontal direction,while the catalyst convection velocity has the same variation regularity in the corresponding directions.The variation of temperature difference and convection velocity lead the crystal growth rate in different crystal orientations to change,which directly affects the crystal morphology of the synthetic diamond.The simulation results are consistent with the experimental results,which shows the correctness of the theoretical rational analysis.This work is expected to be able to facilitate the understanding of catalyst structure regulation mechanism on diamond morphology and the providing of an important theoretical basis for the controllable growth of special crystal shape diamond under HPHT process.展开更多
The correct selection of the crystallographic orientation of diamonds is of prime importance to raise the toolthe. In thes paper, a new method for the determination of crystallographic orientations of diamonds-Laser D...The correct selection of the crystallographic orientation of diamonds is of prime importance to raise the toolthe. In thes paper, a new method for the determination of crystallographic orientations of diamonds-Laser DiffractionTechnique(LDT) is introduced. me principle of this methed is discussed and formation mechanism of the diffractionimages is analyzed. The position of each crystal plane and easy-to-grind direction can be directly decided from the pattern of the diffraction picture.展开更多
In this paper, diamond crystallization from carbonyl nickel powders-C and carbonyl nickel powders + Fe–C systems are investigated in detail at a pressure of 6.0 GPa and temperatures ranging from 1410°C–to 1435&...In this paper, diamond crystallization from carbonyl nickel powders-C and carbonyl nickel powders + Fe–C systems are investigated in detail at a pressure of 6.0 GPa and temperatures ranging from 1410°C–to 1435°C by temperature gradient growth. The effects of Fe additive on the crystal morphology are discussed in the diamond crystallization process.Furthermore, Fourier infrared measurement results indicate that the spectrum of the diamond obtained from Ni + Fe–C system after annealing treatment is nearly consistent with that of natural diamond crystal. We believe that this study is of benefit to a further understanding of the growth mechanism of natural diamond.展开更多
A large diamond crystal up to 500μm in diameter with a smooth(100)facet at its top has been synthesized on Mo substrate through microwave plasma chemical vapor deposition(MPCVD).Its morphology and quality were charac...A large diamond crystal up to 500μm in diameter with a smooth(100)facet at its top has been synthesized on Mo substrate through microwave plasma chemical vapor deposition(MPCVD).Its morphology and quality were characterized by scanning electron microscopy(SEM),and the growth mechanism was roughly illustrated from both macroscopic and microscopic viewpoints.It was found that morphological instabilities are a major factor resulting in synthesis of large diamond crystals,moreover,high microwave power density(MPD),high CH4 concentrations,high pressure,high substrate surface temperature and the addition of a small amount of O2 were also necessary for the synthesis of large diamond crystals.展开更多
Diamond single crystals grown from Fe-Ni-C system at high temperature-high pressure (HPHT) usually contain inclusions related to the metallic catalyst. During the diamond growth, the metallic inclusions are trapped by...Diamond single crystals grown from Fe-Ni-C system at high temperature-high pressure (HPHT) usually contain inclusions related to the metallic catalyst. During the diamond growth, the metallic inclusions are trapped by the growth front or are formed through reaction between the contaminants trapped in the diamond. In the present paper, the metallic inclusions related to the catalyst were systematically examined by transmission electron microscopy (TEM). The chemical composition and crystal structure of the metallic inclusions were for the first time determined by selected area electron diffraction pattern (SADP) combined with energy dispersive X-ray spectrometry (EDS). It is shown that the inclusions are mainly composed of orthorhombic FeSi2, fcc (FeNi)23C6, and orthorhombic Fe3C, hexagonal Ni3C.展开更多
The ohmic contact interface between diamond and metal is essential for the application of diamond detectors.Surface modification can significantly affect the contact performance and eliminate the interface polarizatio...The ohmic contact interface between diamond and metal is essential for the application of diamond detectors.Surface modification can significantly affect the contact performance and eliminate the interface polarization effect.However,the radiation stability of a diamond detector is also sensitive to surface modification.In this work,the influence of surface modification technology on a diamond ohmic contact under high-energy radiation was investigated.Before radiation,the specific contact resistivities(ρc)between Ti/Pt/Au-hydrogen-terminated diamond(H-diamond)and Ti/Pt/Au-oxygenterminated diamond(O-diamond)were 2.0×10^(-4)W·cm^(2) and 4.3×10^(-3)Wcm^(2),respectively.After 10 MeV electron radiation,the ρc of Ti/Pt/Au H-diamond and Ti/Pt/Au O-diamond were 5.3×10^(-3)W·cm^(2)and 9.1×10^(-3)W·cm^(2),respectively.The rates of change of ρc of H-diamond and O-diamond after radiation were 2550%and 112%,respectively.The electron radiation promotes bond reconstruction of the diamond surface,resulting in an increase in ρc.展开更多
A single-crystal diamond detector is fabricated to diagnose 14.1 MeV deuterium-tritium(D-T)fusion neutrons.The size of its diamond film is 4.5 mm×4.5 mm×500μm.This film is sandwiched by a flat,strip-pattern...A single-crystal diamond detector is fabricated to diagnose 14.1 MeV deuterium-tritium(D-T)fusion neutrons.The size of its diamond film is 4.5 mm×4.5 mm×500μm.This film is sandwiched by a flat,strip-patterned gold electrode.The dark current of this detector is experimentally measured to be lower than 0.1 nA under an electric field of 30 kV cm^(-1).This diamond detector is used to measure D-T fusion neutrons with a flux of about 7.5×10^(5) s^(-1)cm^(-2).The pronounced peak with a central energy of 8.28 MeV characterizing the^(12)C(n,α)~9Be reaction in the neutron energy spectrum is experimentally diagnosed,and the energy resolution is better than 1.69%,which is the best result reported so far using a diamond detector.A clear peak with a central energy of 6.52 MeV characterizing the^(12)C(n,n')3αreaction is also identified with an energy resolution of better than 7.67%.展开更多
基金Project supported by the National Natural Science Foundation of China (Grant No. 51172089)the Program for New Century Excellent Talents in University of China
文摘A series of diamond crystals doped with hydrogen is successfully synthesized using LiH as the hydrogen source in a catalyst-carbon system at a pressure of 6.0 GPa and temperature ranging from 1255 C to 1350 C.It is shown that the high temperature plays a key role in the incorporation of hydrogen atoms during diamond crystallization.Fourier transform infrared micro-spectroscopy reveals that most of the hydrogen atoms in the synthesized diamond are incorporated into the crystal structure as sp 3-CH 2-symmetric(2850 cm-1) and sp 3 CH 2-antisymmetric vibrations(2920 cm-1).The intensities of these peaks increase gradually with an increase in the content of the hydrogen source in the catalyst.The incorporation of hydrogen impurity leads to a significant shift towards higher frequencies of the Raman peak from 1332.06 cm-1 to 1333.05 cm-1 and gives rise to some compressive stress in the diamond crystal lattice.Furthermore,hydrogen to carbon bonds are evident in the annealed diamond,indicating that the bonds that remain throughout the annealing process and the vibration frequencies centred at 2850 and 2920 cm-1 have no observable shift.Therefore,we suggest that the sp 3 C-H bond is rather stable in diamond crystals.
基金supported by the National Natural Science Foundation of China(Grant No.51172089)the Program for New Century Excellent Talents in University,the Natural Science Foundation of Guizhou Provincial Education Department(Grant No.KY[2013]183)the Collaborative Fund of Science and Technology Office of Guizhou Province,China(Grant No.LH[2015]7232)
文摘The effect of the catalyst height on the morphology of diamond crystal is investigated by means of temperature gradient growth(TGG) under high pressure and high temperature(HPHT) conditions with using a Ni-based catalyst in this article. The experimental results show that the morphology of diamond changes from an octahedral shape to a cuboctahedral shape as the catalyst height rises. Moreover, the finite element method(FEM) is used to simulate the temperature field of the melted catalyst/solvent. The results show that the temperature at the location of the seed diamond continues to decrease with the increase of catalyst height, which is conducive to changing the morphology of diamond. This work provides a new way to change the diamond crystal morphology.
基金Project supported by the National Natural Science Foundation of China (Grant No.50572032)
文摘Additive Ba(N 3) 2 as a source of nitrogen is heavily doped into the graphite-Fe-based alloy system to grow nitrogendoped diamond crystals under a relatively high pressure (about 6.0 GPa) by employing the temperature gradient method.Gem-grade diamond crystal with a size of around 5 mm and a nitrogen concentration of about 1173 ppm is successfully synthesised for the first time under high pressure and high temperature in a China-type cubic anvil highpressure apparatus.The growth habit of diamond crystal under the environment with high degree of nitrogen doping is investigated.It is found that the morphologies of heavily nitrogen-doped diamond crystals are all of octahedral shape dominated by {111} facets.The effects of temperature and duration on nitrogen concentration and form are explored by infrared absorption spectra.The results indicate that nitrogen impurity is present in diamond predominantly in the dispersed form accompanied by aggregated form,and the aggregated nitrogen concentration in diamond increases with temperature and duration.In addition,it is indicated that nitrogen donors are more easily incorporated into growing crystals at higher temperature.Strains in nitrogen-doped diamond crystal are characterized by micro-Raman spectroscopy.Measurement results demonstrate that the undoped diamond crystals exhibit the compressive stress,whereas diamond crystals heavily doped with the addition of Ba(N 3) 2 display the tensile stress.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 51071074, 51172089, and 51171070)the Program for New Century Excellent Talents in University of Ministry of Education of China
文摘We investigate the temperature field variation in the growth region of a diamond crystal in a sealed cell during the whole process of crystal growth by using the temperature gradient method (TGM) at high pressure and high temperature (HPHT). We employ both the finite element method (FEM) and in situ experiments. Simulation results show that the temperature in the center area of the growth cell continues to decrease during the process of large diamond crystal growth. These results are in good agreement with our experimental data, which demonstrates that the finite element model can successfully predict the temperature field variations in the growth cell. The FEM simulation will be useful to grow larger high-quality diamond crystal by using the TGM. Furthermore, this method will be helpful in designing better cells and improving the growth process of gem-quality diamond crystal.
基金Project supported by the Natural Science Foundation of Heilongjiang Province,China(Grant No.E201341)the Open Research Program of Key Lab of Superhard Materials of Mudanjiang Normal College,China(Grant No.201302)
文摘In this paper, we have reported an investigation on the evolution of nitrogen structures in diamond crystals which contain nitrogen donor atoms in the range of 1500 ppm–1600 ppm following an annealing treatment at a high pressure of about 6.5 GPa and high temperatures of 1920 K–2120 K. The annealing treatment was found to completely transform nitrogen atoms originally arranged in a single substitutional form(C-center), into a pair form(A-center), indicated from infrared(IR) spectra. The photoluminescence(PL) spectra revealed that a small fraction of nitrogen atoms remained in C-center form, while some nitrogen atoms in A-center form were further transformed into N3 and H3 center structures. In addition, PL spectra have revealed the existence of two newly observed nitrogen-related structures with zero phonon lines at 611 nm and 711 nm. All these findings above are very helpful in understanding the formation mechanism of natural diamond stones of the Ia-type, which contains nitrogen atoms in an aggregated form.
基金Project supported by the National Natural Science Foundation of China (Grant No. 50572032)
文摘This paper reprots that with Ni-based catalyst/solvent and with a dopant of NaN 3,large green single crystal diamonds with perfect shape are successfully synthesized by temperature gradient method under high pressure and high temperature in a China-type cubic anvil high-pressure apparatus (SPD-6×1200),and the highest nitrogen concentration reaches approximately 1214-1257 ppm calculated by infrared absorption spectra.The synthesis conditions are about 5.5 GPa and 1240-1300 C.The growth behaviour of diamond with high-nitrogen concentration is investigated in detail.The results show that,with increasing the content of NaN 3 added in synthesis system,the width of synthesis temperature region for growth high-quality diamonds becomes narrower,and the morphology of diamond crystal is changed from cube-octahedral to octahedral at same temperature and pressure,the crystal growth rate is slowed down,nevertheless,the nitrogen concentration doped in synthetic diamond increases.
基金Supported by the National Natural Science Foundation of China under Grant No 50972084the Natural Science Foundation of Shandong Province under Grant No ZR2010EM050.
文摘Diamond is synthesized in an Fe-Ni-C system at high pressure and high temperature,the C sp^(3) content profile through different thicknesses of interface between diamond and the catalyst film is measured by using electron energy loss spectroscopy.It is found that the Csp^(3) content varies from 87.33% to 78.15% when the measured position is located at the inner face near the diamond and then changes to 6 μm further away.Transmission electron microscope examinations show that there are different phases in the interface,such as Fe3C,γ-(Fe,Ni),and graphite,but the graphite phase diminishes gradually towards the inner face of the interface.These results profoundly indicate that the carbon atoms,required for diamond growth,could only come from the carbon-rich phase,Fe3C,but not directly from the graphite.It is possible that carbon atoms from the graphite in the interface first react with Fe atoms to produce carbide Fe3 C during diamond synthesis at high pressure and high temperature.The Fe3 C finally decomposes into carbon atoms with the sp^(3) electron state at the interface to form the diamond.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 50572032 and 50731006)
文摘In this paper,we report on the influence of annealing treatment on as-grown Ib-type diamond crystal under high pressure and high temperature in a china-type cubic anvil high-pressure apparatus.Experiments are carried out at a pressure of 7.0 GPa and temperatures ranging from 1700 C to 1900 C for 1 h.Annealing treatment of the diamond crystal shows that the aggregation rate constant of nitrogen atoms in the as-grown Ib-type diamond crystal strongly depends on diamond morphology and annealing temperature.The aggregation rate constant of nitrogen remarkably increases with the increase of annealing temperature and its value in octahedral diamond is much higher than that in cubic diamond annealed at the same temperature.The colour of octahedral diamond crystal is obviously reduced from yellow to nearly colorless after annealing treatment for 1 h at 1900 C,which is induced by nitrogen aggregation in a diamond lattice.The extent of nitrogen aggregation in an annealed diamond could approach approximately 98% indicated from the infrared absorption spectra.The micro-Raman spectrum reveals that the annealing treatment can improve the crystalline quality of Ib-type diamond characterized by a half width at full maximum at first order Raman peak,and therefore the annealed diamond crystals exhibit nearly the same properties as the natural IaA-type diamond stones of high quality in the Raman measurements.
基金Thi work was supported by the Nstional Natural ScienceFoundation of China (Grant. No 593T1027).
文摘Some dislocations, which are generated in the diamond single crystal during the diamond crystal growth from Fe-Ni-C system, may affect diamond crystal growth mode at high temperature-high pressure (HPHT). The concentric dislocation loops were successfully examined by Moire images. The surface morphologies of growing and as-grown diamond single crystals were observed by scanning electron microscopy (SEM). The concentric dislocation loops formation process and their effect on the diamond crystal growth mode were analyzed. It should be noted that whatever the nature of the dislocation is, should the Burgers vector of dislocation has a component at the direction normal to the growth interface, the dislocation will make the face parallel to the growth interface grow into spiral face. The presence of consecutive spiral steps on the diamond crystal surface also provides a direct evidence of the dislocation mechanism of diamond crystal growth.
基金Project supported by the National Natural Science Foundation of China (Grant No. 51172089)the Program for New Century Excellent Talents in University,China
文摘In this paper,we explore diamond synthesis with a series of experiments using an Fe-Ni catalyst and a P3N5 additive in the temperature range of 1250-1550 ℃ and the pressure range of 5.0-6.3 GPa.We also investigate the influence of nitrogen on diamond crystallization.Our results show that the synthesis conditions(temperature and pressure) increase with the amount of P3N5 additive increasing.The nitrogen impurity can significantly influence the diamond morphology.The diamonds stably grow into strip and lamellar shapes in the nitrogen-rich environment.The Fourier-transform infrared spectrum shows that the nitrogen concentration increases rapidly with the content of P3N5 additive increasing.By spectrum analysis,we find that with the increase of the nitrogen concentration,the Ib-type nitrogen atoms can aggregate in the A-centre form.The highest A-centre nitrogen concentration is approximately 840 ppm.
基金Project supported by the National Natural Science Foundation of China (Grant No. 51172089)the Graduate Innovation Fund of Jilin University (Grant No. 20111022)
文摘In this paper,the diamond epitaxial growth mechanism has been studied in detail by employing several types of diamond as a seed in a catalyst-graphite system under high pressure and high temperature (HPHT) conditions.We find that the diamond nucleation,growth rate,crystal orientation,and morphology are significantly influenced by the original seeds.The smooth surfaces of seeds are beneficial for the fabrication of high-quality diamond.Our results reveal that the diamond morphology is mainly determined by the original shape of seeds in the early growth stage,but it has an adjustment process during the growth and leads to well symmetry.Additionally,we have also established the growth model for the twinned diamond grown on several seeds,and proposed the possible growth processes by tracking the particular shapes of seeds before and after treatment under HPHT conditions.These results suggest that the shape-controlled synthesis of diamond with well morphology can be realized by employing certain suitable diamond seeds.This work is expected to play an important role in the preparation of trustworthy diamond-based electronic and photonic devices.
基金Project supported by the National Natural Science Foundation of China(Grant No.11804305)the Natural Science Foundation of Chongqing,China(Grant No.cstc2019jcyj-msxmX0391)+1 种基金the Science and Technology Research Program of Chongqing Municipal Education Commission,China(Grant No.KJ201901405)the Open Project of State Key Laboratory of Superhard Materials,Jilin University,China(Grant No.201912).
文摘To elucidate the regulation mechanism of catalyst geometry structure to diamond growth,we establish three catalyst modes with different structures.The simulation results show that with the decrease of the protruding height of the catalyst,the low-temperature region gradually moves toward the center of the catalyst,which causes the distribution characteristics of the temperature and convection field in the catalyst to change.The temperature difference in vertical direction of the catalyst decreases gradually and increases in the horizontal direction,while the catalyst convection velocity has the same variation regularity in the corresponding directions.The variation of temperature difference and convection velocity lead the crystal growth rate in different crystal orientations to change,which directly affects the crystal morphology of the synthetic diamond.The simulation results are consistent with the experimental results,which shows the correctness of the theoretical rational analysis.This work is expected to be able to facilitate the understanding of catalyst structure regulation mechanism on diamond morphology and the providing of an important theoretical basis for the controllable growth of special crystal shape diamond under HPHT process.
文摘The correct selection of the crystallographic orientation of diamonds is of prime importance to raise the toolthe. In thes paper, a new method for the determination of crystallographic orientations of diamonds-Laser DiffractionTechnique(LDT) is introduced. me principle of this methed is discussed and formation mechanism of the diffractionimages is analyzed. The position of each crystal plane and easy-to-grind direction can be directly decided from the pattern of the diffraction picture.
基金supported by the National Natural Science Foundation of China(Grant No.51172089)the Natural Science Foundation of Guizhou Provincial Education Department,China(Grant No.KY[2013]183)the Research Fund for the Doctoral Program of Tongren University,China(Grant Nos.DS1302 and trxy S1415)
文摘In this paper, diamond crystallization from carbonyl nickel powders-C and carbonyl nickel powders + Fe–C systems are investigated in detail at a pressure of 6.0 GPa and temperatures ranging from 1410°C–to 1435°C by temperature gradient growth. The effects of Fe additive on the crystal morphology are discussed in the diamond crystallization process.Furthermore, Fourier infrared measurement results indicate that the spectrum of the diamond obtained from Ni + Fe–C system after annealing treatment is nearly consistent with that of natural diamond crystal. We believe that this study is of benefit to a further understanding of the growth mechanism of natural diamond.
基金supported by National Natural Science Foundation of China(No.11175137)
文摘A large diamond crystal up to 500μm in diameter with a smooth(100)facet at its top has been synthesized on Mo substrate through microwave plasma chemical vapor deposition(MPCVD).Its morphology and quality were characterized by scanning electron microscopy(SEM),and the growth mechanism was roughly illustrated from both macroscopic and microscopic viewpoints.It was found that morphological instabilities are a major factor resulting in synthesis of large diamond crystals,moreover,high microwave power density(MPD),high CH4 concentrations,high pressure,high substrate surface temperature and the addition of a small amount of O2 were also necessary for the synthesis of large diamond crystals.
文摘Diamond single crystals grown from Fe-Ni-C system at high temperature-high pressure (HPHT) usually contain inclusions related to the metallic catalyst. During the diamond growth, the metallic inclusions are trapped by the growth front or are formed through reaction between the contaminants trapped in the diamond. In the present paper, the metallic inclusions related to the catalyst were systematically examined by transmission electron microscopy (TEM). The chemical composition and crystal structure of the metallic inclusions were for the first time determined by selected area electron diffraction pattern (SADP) combined with energy dispersive X-ray spectrometry (EDS). It is shown that the inclusions are mainly composed of orthorhombic FeSi2, fcc (FeNi)23C6, and orthorhombic Fe3C, hexagonal Ni3C.
基金Project supported by the National Key Research and Development Program of China(Grant No.2022YFB3608601).
文摘The ohmic contact interface between diamond and metal is essential for the application of diamond detectors.Surface modification can significantly affect the contact performance and eliminate the interface polarization effect.However,the radiation stability of a diamond detector is also sensitive to surface modification.In this work,the influence of surface modification technology on a diamond ohmic contact under high-energy radiation was investigated.Before radiation,the specific contact resistivities(ρc)between Ti/Pt/Au-hydrogen-terminated diamond(H-diamond)and Ti/Pt/Au-oxygenterminated diamond(O-diamond)were 2.0×10^(-4)W·cm^(2) and 4.3×10^(-3)Wcm^(2),respectively.After 10 MeV electron radiation,the ρc of Ti/Pt/Au H-diamond and Ti/Pt/Au O-diamond were 5.3×10^(-3)W·cm^(2)and 9.1×10^(-3)W·cm^(2),respectively.The rates of change of ρc of H-diamond and O-diamond after radiation were 2550%and 112%,respectively.The electron radiation promotes bond reconstruction of the diamond surface,resulting in an increase in ρc.
基金supported by National Natural Science Foundation of China(No.12075241)。
文摘A single-crystal diamond detector is fabricated to diagnose 14.1 MeV deuterium-tritium(D-T)fusion neutrons.The size of its diamond film is 4.5 mm×4.5 mm×500μm.This film is sandwiched by a flat,strip-patterned gold electrode.The dark current of this detector is experimentally measured to be lower than 0.1 nA under an electric field of 30 kV cm^(-1).This diamond detector is used to measure D-T fusion neutrons with a flux of about 7.5×10^(5) s^(-1)cm^(-2).The pronounced peak with a central energy of 8.28 MeV characterizing the^(12)C(n,α)~9Be reaction in the neutron energy spectrum is experimentally diagnosed,and the energy resolution is better than 1.69%,which is the best result reported so far using a diamond detector.A clear peak with a central energy of 6.52 MeV characterizing the^(12)C(n,n')3αreaction is also identified with an energy resolution of better than 7.67%.
