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...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 cub- octahedral 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（N3）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 temperatur...Additive Ba（N3）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（N3）2 display the tensile stress.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 h...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 NAN3, 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 NAN3, 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 121-1257 ppm calculated by infrared absorption spectra. The synthesis conditions are about 5.5 CPa and 1240-1300 ℃. The growth behaviour of diamond with high-nitrogen concentration is investigated in detail. The results show that, with increasing the content of NaN3 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
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
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
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 an...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
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
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
Diamond is a highly valuable material with diverse industrial applications,particularly in the fields of semiconductor,optics,and high-power electronics.However,its high hardness and chemical stability make it difficu...Diamond is a highly valuable material with diverse industrial applications,particularly in the fields of semiconductor,optics,and high-power electronics.However,its high hardness and chemical stability make it difficult to realize high-efficiency and ultra-low damage machining of diamond.To address these challenges,several polishing methods have been developed for both single crystal diamond(SCD)and polycrystalline diamond(PCD),including mechanical,chemical,laser,and ion beam processing methods.In this review,the characteristics and application scope of various polishing technologies for SCD and PCD are highlighted.Specifically,various energy beam-based direct and assisted polishing technologies,such as laser polishing,ion beam polishing,plasma-assisted polishing,and laser-assisted polishing,are summarized.The current research progress,material removal mechanism,and infuencing factors of each polishing technology are analyzed.Although some of these methods can achieve high material removal rates or reduce surface roughness,no single method can meet all the requirements.Finally,the future development prospects and application directions of different polishing technologies are presented.展开更多
The lattice constants of diamond and graphite at high pressure and high temperature (HPHT) were calculated on the basis of linear expansion coefficient and elastic constant. According to the empirical electron theory ...The lattice constants of diamond and graphite at high pressure and high temperature (HPHT) were calculated on the basis of linear expansion coefficient and elastic constant. According to the empirical electron theory of solids and molecules (EET), the valence electron structures (VESs) of diamond, graphite crystal and their common planes were calculated. The relationship between diamond and graphite structure was analyzed based on the boundary condition of the improved Thomas-Fermi-Dirac theory by Cheng (TFDC). It was found that the electron densities of common planes in graphite were not continuous with those of planes in diamond at the first order of approximation. The results show that during the course of diamond single crystal growth at HPHT with metal catalyst, the carbon sources forming diamond structure do not come from the graphite structure directly. The diamond growth mechanism was discussed from the viewpoint of valence electron structure.展开更多
The inclusions in large diamond single crystals have effects on its ultimate performance, which restricts its industrial applications to a great extent. Therefore, it is necessary to study the inclusions systematicall...The inclusions in large diamond single crystals have effects on its ultimate performance, which restricts its industrial applications to a great extent. Therefore, it is necessary to study the inclusions systematically. In this paper, large diamond single crystals with different content values of inclusions are synthesized along the(100) surface by the temperature gradient method(TGM) under 5.6 GPa at different temperatures. With the synthetic temperature changing from 1200?C to 1270?C,the shapes of diamonds change from plate to low tower, to high tower, even to steeple. From the microscopic photographs of the diamond samples, it can be observed that with the shapes of the samples changing at different temperatures, the content values of inclusions in diamonds become zero, a little, much and most, correspondingly. Consequently, with the temperature growing from low to high, the content values of inclusions in crystals increase. The origin of inclusions is explained by the difference in growth rate between diamond crystal and its surface. The content values of inclusions in diamond samples are quantitatively calculated by testing the densities of diamond samples. And the composition and inclusion content are analyzed by energy dispersive spectroscopy(EDS) and x-ray diffraction(XRD). From contrasting scanning electron microscopy(SEM) photographs, it can be found that the more the inclusions in diamond, the more imperfect the diamond surface is.展开更多
The synthesis of diamond single crystal in the Fe64Ni36-C system with h-BN additive is investigated at pressure 6.5 GPa and temperature range of 1300-1400℃. The color of the obtained diamond crystals translates from ...The synthesis of diamond single crystal in the Fe64Ni36-C system with h-BN additive is investigated at pressure 6.5 GPa and temperature range of 1300-1400℃. The color of the obtained diamond crystals translates from yellow to dark green with increasing the h-BN addition. Fourier-transform infrared （FTIR） results indicate that sp2 hybridization B-N-B and B-N structures generate when the additive content reaches a certain value in the system. The two peaks are located at 745 and 1425cm-1, respectively. Fhrthermore, the FTIR characteristic peak resulting from nitrogen pairs is noticed and it tends to vanish when the h-BN addition reaches 1.1 wt%. Furthermore, Raman peak of the synthesized diamond shifts down to a lower wavenumber with increasing the h-BN ~ddition content in the synthesis system.展开更多
A novel method was developed to deposit a large crystal diamond with good facets up to 1000 μm on a tungsten substrate using a microwave plasma enhanced chemical vapor deposition （MPCVD）. This method consists of tw...A novel method was developed to deposit a large crystal diamond with good facets up to 1000 μm on a tungsten substrate using a microwave plasma enhanced chemical vapor deposition （MPCVD）. This method consists of two steps, namely single-crystal nucleation and growth. Prior to the fabrication of the well-faceted, large crystal diamond, an investigation was made into the nucleation and growth of the diamond which were affected by the O2 concentration and substrate temperature. Deposited diamond crystals were characterized by scanning electron microscopy and micro-Raman spectroscopy. The results showed that the conditions of single-crystal nucleation were appropriate when the ratio of H2/CH4/O2 was about 200/7.0/2.0, while the sub- strate temperature Ts of 1000℃ to 1050℃ was the appropriate range for single-crystal diamond growth. Under the optimum parameters, a well-faeeted large crystal diamond was obtained.展开更多
A diamond single crystal, which was synthesized at a high temperature of 1570 K and a high pressure of 5.5 GPa in a Fe-Ni-C system, was directly and systematically examined by transmission electron microscopy (TEM). I...A diamond single crystal, which was synthesized at a high temperature of 1570 K and a high pressure of 5.5 GPa in a Fe-Ni-C system, was directly and systematically examined by transmission electron microscopy (TEM). It is proposed that there exists a variety of imperfections such as dislocation loops, stacking faults, twins and stacking-fault tetrahedral in the diamond, which may be derived from the supersaturated vacancies generated during rapid cooling from high temperature. The formation process of the imperfections is discussed briefly.展开更多
Although atom configuration in crystals is precisely known thanks to imaging techniques, there is no experimental way to know the exact location of bonds or charges. Many different representations have been proposed, ...Although atom configuration in crystals is precisely known thanks to imaging techniques, there is no experimental way to know the exact location of bonds or charges. Many different representations have been proposed, yet no theory to unify conceptions. The present paper describes methods to derive bonds and charge location in double-face-centered cubic crystals with 4 and 6 atoms per unit cell using two novel rules introduced in earlier works: the even-odd and the isoelectronicity rules. Both of these rules were previously applied to ions, molecules and some solids, and the even-odd rule was also tested on two covalent crystal structures: centered-cubic and single-face-centered cubic crystals. In the present study, the diamond-like structure was subjected to the isoelectronicity rule in order to derive Zinc-blende structures. Rock-salt-like crystals were derived from each other using both rules. These structures represent together more than 230 different crystals. Findings for these structures are threefold: both rules describe a very sure method to obtain valid single covalent-bonded structures;single covalent structures can be used in every case instead of the classical ionic model;covalent bonds and charges positions do not have any relation with the valence number given in the periodic table.展开更多
This paper studies the abrasion mechanism of natural diamond crystals,proposes a new theory on soft and hard directions to grind diamonds in different planes.Examination of the micro-structure of polished surface by S...This paper studies the abrasion mechanism of natural diamond crystals,proposes a new theory on soft and hard directions to grind diamonds in different planes.Examination of the micro-structure of polished surface by SEM shows diamond is mainly removed through a micro-cleavage process in (111) planes and the abrasion resistance of diamond relates to the orientation of cleavage planes,and the abrasion resistance anisotropy of diamond crystals is mainly due to the different levels of difficulty in micro-cleavage,while they are lapped in different directions.The results of analysis are in conformance with experimental results.展开更多
Optical centers of single-crystal diamond grown by DC arc plasma jet chemical vapor deposition(CVD) were examined using a low-temperature photoluminescence(PL) technique. The results show that most of the nitrogen-vac...Optical centers of single-crystal diamond grown by DC arc plasma jet chemical vapor deposition(CVD) were examined using a low-temperature photoluminescence(PL) technique. The results show that most of the nitrogen-vacancy(NV) complexes are present as NV-centers, although some H2 and H3 centers and B-aggregates are also present in the single-crystal diamond because of nitrogen aggregation resulting from high N_2 incorporation and the high mobility of vacancies under growth temperatures of 950–1000°C. Furthermore, emissions of radiation-induced defects were also detected at 389, 467.5, 550, and 588.6 nm in the PL spectra. The reason for the formation of these radiation-induced defects is not clear. Although a Ni-based alloy was used during the diamond growth, Ni-related emissions were not detected in the PL spectra. In addition, the silicon-vacancy(Si-V)-related emission line at 737 nm, which has been observed in the spectra of many previously reported microwave plasma chemical vapor deposition(MPCVD) synthetic diamonds, was absent in the PL spectra of the single-crystal diamond prepared in this work. The high density of NV-centers, along with the absence of Ni-related defects and Si-V centers, makes the single-crystal diamond grown by DC arc plasma jet CVD a promising material for applications in quantum computing.展开更多
We report the simultaneous enlarged growth of seven single crystal diamond(SCD) plates free from polycrystalline diamond(PCD) rim by using a microwave plasma chemical vapor deposition(MPCVD) system. Optical microscope...We report the simultaneous enlarged growth of seven single crystal diamond(SCD) plates free from polycrystalline diamond(PCD) rim by using a microwave plasma chemical vapor deposition(MPCVD) system. Optical microscope and atomic force microscope(AFM) show the typical step-bunching SCD morphology at the center, edge, and corner of the samples. The most aggressively expanding sample shows a top surface area three times of that of the substrate. The effective surface expanding is attributed to the utilization of the diamond substrates with(001) side surfaces, the spacial isolation of them to allow the sample surface expanding, and the adoption of the reported pocket holder. Nearly constant temperature of the diamond surfaces is maintained during growth by only decreasing the sample height, and thus all the other growth parameters can be kept unchanged to achieve high quality SCDs. The SCDs have little stress as shown by the Raman spectra. The full width at half maximum(FWHM) data of both the Raman characteristic peak and(004) x-ray rocking curve of the samples are at the same level as those of the standard CVD SCD from Element Six Ltd. The nonuniformity of the sample thickness or growth rate is observed, and photoluminescence spectra show that the nitrogen impurity increases with increasing growth rate. It is found that the reduction of the methane ratio in the sources gas flow from 5% to 3% leads to decrease of the vertical growth rate and increase of the lateral growth rate. This is beneficial to expand the top surface and improve the thickness uniformity of the samples. At last, the convenience of the growth method transferring to massive production has also been demonstrated by the successful simultaneous enlarged growth of 14 SCD samples.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 cub- octahedral 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（N3）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（N3）2 display the tensile stress.
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 NAN3, 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 121-1257 ppm calculated by infrared absorption spectra. The synthesis conditions are about 5.5 CPa and 1240-1300 ℃. The growth behaviour of diamond with high-nitrogen concentration is investigated in detail. The results show that, with increasing the content of NaN3 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 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sponsored by the National Natural Science Foundation of China(Nos.51835004,U22A20198)the Major Science and Technology Projects in Henan Province(221100230300)the 111 Project(No.B23011)。
文摘Diamond is a highly valuable material with diverse industrial applications,particularly in the fields of semiconductor,optics,and high-power electronics.However,its high hardness and chemical stability make it difficult to realize high-efficiency and ultra-low damage machining of diamond.To address these challenges,several polishing methods have been developed for both single crystal diamond(SCD)and polycrystalline diamond(PCD),including mechanical,chemical,laser,and ion beam processing methods.In this review,the characteristics and application scope of various polishing technologies for SCD and PCD are highlighted.Specifically,various energy beam-based direct and assisted polishing technologies,such as laser polishing,ion beam polishing,plasma-assisted polishing,and laser-assisted polishing,are summarized.The current research progress,material removal mechanism,and infuencing factors of each polishing technology are analyzed.Although some of these methods can achieve high material removal rates or reduce surface roughness,no single method can meet all the requirements.Finally,the future development prospects and application directions of different polishing technologies are presented.
基金the National Natural Science Foundation of China (Grant Nos. 50371048 and 50372035)the Natural Science Foundation of Shandong Province of China (Grant No. Y2007F11)
文摘The lattice constants of diamond and graphite at high pressure and high temperature (HPHT) were calculated on the basis of linear expansion coefficient and elastic constant. According to the empirical electron theory of solids and molecules (EET), the valence electron structures (VESs) of diamond, graphite crystal and their common planes were calculated. The relationship between diamond and graphite structure was analyzed based on the boundary condition of the improved Thomas-Fermi-Dirac theory by Cheng (TFDC). It was found that the electron densities of common planes in graphite were not continuous with those of planes in diamond at the first order of approximation. The results show that during the course of diamond single crystal growth at HPHT with metal catalyst, the carbon sources forming diamond structure do not come from the graphite structure directly. The diamond growth mechanism was discussed from the viewpoint of valence electron structure.
基金Project supported by the Natural Science Foundation of Henan Province,China(Grant No.182300410279)the Key Science and Technology Research Project of Henan Province,China(Grant No.182102210311)+2 种基金the Key Scientific Research Project in Colleges and Universities of Henan Province,China(Grant No.18A430017)the Professional Practice Demonstration Base Program for Professional Degree Graduate in Material Engineering of Henan Polytechnic University,China(Grant No.2016YJD03)the Fund for the Innovative Research Team(in Science and Technology)in the University of Henan Province,China(Grant No.19IRTSTHN027)
文摘The inclusions in large diamond single crystals have effects on its ultimate performance, which restricts its industrial applications to a great extent. Therefore, it is necessary to study the inclusions systematically. In this paper, large diamond single crystals with different content values of inclusions are synthesized along the(100) surface by the temperature gradient method(TGM) under 5.6 GPa at different temperatures. With the synthetic temperature changing from 1200?C to 1270?C,the shapes of diamonds change from plate to low tower, to high tower, even to steeple. From the microscopic photographs of the diamond samples, it can be observed that with the shapes of the samples changing at different temperatures, the content values of inclusions in diamonds become zero, a little, much and most, correspondingly. Consequently, with the temperature growing from low to high, the content values of inclusions in crystals increase. The origin of inclusions is explained by the difference in growth rate between diamond crystal and its surface. The content values of inclusions in diamond samples are quantitatively calculated by testing the densities of diamond samples. And the composition and inclusion content are analyzed by energy dispersive spectroscopy(EDS) and x-ray diffraction(XRD). From contrasting scanning electron microscopy(SEM) photographs, it can be found that the more the inclusions in diamond, the more imperfect the diamond surface is.
基金Supported by the National Natural Science Foundation of China under Grant No 51172089the Natural Science Foundation of Guizhou Province Education Department under Grant No KY[2013]183the Natural Science Foundation of Guizhou Province Science and Technology Agency under Grant Nos LH[2015]7232 and LH[2015]7228
文摘The synthesis of diamond single crystal in the Fe64Ni36-C system with h-BN additive is investigated at pressure 6.5 GPa and temperature range of 1300-1400℃. The color of the obtained diamond crystals translates from yellow to dark green with increasing the h-BN addition. Fourier-transform infrared （FTIR） results indicate that sp2 hybridization B-N-B and B-N structures generate when the additive content reaches a certain value in the system. The two peaks are located at 745 and 1425cm-1, respectively. Fhrthermore, the FTIR characteristic peak resulting from nitrogen pairs is noticed and it tends to vanish when the h-BN addition reaches 1.1 wt%. Furthermore, Raman peak of the synthesized diamond shifts down to a lower wavenumber with increasing the h-BN ~ddition content in the synthesis system.
基金supported by the Natural Science Foundation of Hubei Province of China(2008CDB255)the Educational Commission of Hubei Province of China(No.Q20081505)the Key Laboratory for Green Chemical Process of the Ministry of Education of China (No.RGCT200801)
文摘A novel method was developed to deposit a large crystal diamond with good facets up to 1000 μm on a tungsten substrate using a microwave plasma enhanced chemical vapor deposition （MPCVD）. This method consists of two steps, namely single-crystal nucleation and growth. Prior to the fabrication of the well-faceted, large crystal diamond, an investigation was made into the nucleation and growth of the diamond which were affected by the O2 concentration and substrate temperature. Deposited diamond crystals were characterized by scanning electron microscopy and micro-Raman spectroscopy. The results showed that the conditions of single-crystal nucleation were appropriate when the ratio of H2/CH4/O2 was about 200/7.0/2.0, while the sub- strate temperature Ts of 1000℃ to 1050℃ was the appropriate range for single-crystal diamond growth. Under the optimum parameters, a well-faeeted large crystal diamond was obtained.
文摘A diamond single crystal, which was synthesized at a high temperature of 1570 K and a high pressure of 5.5 GPa in a Fe-Ni-C system, was directly and systematically examined by transmission electron microscopy (TEM). It is proposed that there exists a variety of imperfections such as dislocation loops, stacking faults, twins and stacking-fault tetrahedral in the diamond, which may be derived from the supersaturated vacancies generated during rapid cooling from high temperature. The formation process of the imperfections is discussed briefly.
文摘Although atom configuration in crystals is precisely known thanks to imaging techniques, there is no experimental way to know the exact location of bonds or charges. Many different representations have been proposed, yet no theory to unify conceptions. The present paper describes methods to derive bonds and charge location in double-face-centered cubic crystals with 4 and 6 atoms per unit cell using two novel rules introduced in earlier works: the even-odd and the isoelectronicity rules. Both of these rules were previously applied to ions, molecules and some solids, and the even-odd rule was also tested on two covalent crystal structures: centered-cubic and single-face-centered cubic crystals. In the present study, the diamond-like structure was subjected to the isoelectronicity rule in order to derive Zinc-blende structures. Rock-salt-like crystals were derived from each other using both rules. These structures represent together more than 230 different crystals. Findings for these structures are threefold: both rules describe a very sure method to obtain valid single covalent-bonded structures;single covalent structures can be used in every case instead of the classical ionic model;covalent bonds and charges positions do not have any relation with the valence number given in the periodic table.
文摘This paper studies the abrasion mechanism of natural diamond crystals,proposes a new theory on soft and hard directions to grind diamonds in different planes.Examination of the micro-structure of polished surface by SEM shows diamond is mainly removed through a micro-cleavage process in (111) planes and the abrasion resistance of diamond relates to the orientation of cleavage planes,and the abrasion resistance anisotropy of diamond crystals is mainly due to the different levels of difficulty in micro-cleavage,while they are lapped in different directions.The results of analysis are in conformance with experimental results.
基金financially supported by the International Science and Technology Cooperation Program of China (No.2015DFG02100)the National Key Laboratory of Shock Wave and Detonation Physics (LSD) Project (No.YK20150101001)
文摘Optical centers of single-crystal diamond grown by DC arc plasma jet chemical vapor deposition(CVD) were examined using a low-temperature photoluminescence(PL) technique. The results show that most of the nitrogen-vacancy(NV) complexes are present as NV-centers, although some H2 and H3 centers and B-aggregates are also present in the single-crystal diamond because of nitrogen aggregation resulting from high N_2 incorporation and the high mobility of vacancies under growth temperatures of 950–1000°C. Furthermore, emissions of radiation-induced defects were also detected at 389, 467.5, 550, and 588.6 nm in the PL spectra. The reason for the formation of these radiation-induced defects is not clear. Although a Ni-based alloy was used during the diamond growth, Ni-related emissions were not detected in the PL spectra. In addition, the silicon-vacancy(Si-V)-related emission line at 737 nm, which has been observed in the spectra of many previously reported microwave plasma chemical vapor deposition(MPCVD) synthetic diamonds, was absent in the PL spectra of the single-crystal diamond prepared in this work. The high density of NV-centers, along with the absence of Ni-related defects and Si-V centers, makes the single-crystal diamond grown by DC arc plasma jet CVD a promising material for applications in quantum computing.
基金Project supported by the National Key Research and Development Program of China(Grant Nos.2018YFB0406504 and 2016YFB0400105)the National Postdoctoral Program for Innovative Talents,China(Grant No.BX20190263)
文摘We report the simultaneous enlarged growth of seven single crystal diamond(SCD) plates free from polycrystalline diamond(PCD) rim by using a microwave plasma chemical vapor deposition(MPCVD) system. Optical microscope and atomic force microscope(AFM) show the typical step-bunching SCD morphology at the center, edge, and corner of the samples. The most aggressively expanding sample shows a top surface area three times of that of the substrate. The effective surface expanding is attributed to the utilization of the diamond substrates with(001) side surfaces, the spacial isolation of them to allow the sample surface expanding, and the adoption of the reported pocket holder. Nearly constant temperature of the diamond surfaces is maintained during growth by only decreasing the sample height, and thus all the other growth parameters can be kept unchanged to achieve high quality SCDs. The SCDs have little stress as shown by the Raman spectra. The full width at half maximum(FWHM) data of both the Raman characteristic peak and(004) x-ray rocking curve of the samples are at the same level as those of the standard CVD SCD from Element Six Ltd. The nonuniformity of the sample thickness or growth rate is observed, and photoluminescence spectra show that the nitrogen impurity increases with increasing growth rate. It is found that the reduction of the methane ratio in the sources gas flow from 5% to 3% leads to decrease of the vertical growth rate and increase of the lateral growth rate. This is beneficial to expand the top surface and improve the thickness uniformity of the samples. At last, the convenience of the growth method transferring to massive production has also been demonstrated by the successful simultaneous enlarged growth of 14 SCD samples.
