Type IIa Diamond Research Articles

Observation of Whispering-Gallery Modes in a Diamond Microsphere

We demonstrate a Type Ib diamond (nitrogen impurity of >5 ppm) microsphere whispering-gallery mode resonator in the near-infrared wavelengths between 1426.10 nm and 1427.42 nm in the 90° elastic-light-scattering for both transverse magnetic (TM) and transverse electric (TE) polarizations. The highest measured whispering-gallery mode quality-factor is in the order of 10 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sup> , and the mode spacing is 0.332 nm both for TM and TE polarizations. The coupling of the continuous-wave tunable infrared excitation laser to the diamond microsphere is achieved by a single-mode silica optical-fiber half-coupler. Such a diamond resonator can further be used as stable optical-frequency-comb generating or lasing microcavities by exploiting the nitrogen-vacancy centers present within the diamond.

Effects of cooling process on qualities of Gem-diamond single crystals

In the paper, under 5.6 GPa and 1200-1400℃, the type Ib diamond single crystals on defect-free[111] -oriented seed crystals are synthesized in a cubic anvil under high pressure and high temperature when the crack problem of diamond single crystal appears frequently. Highpurity Fe-Ni-Co solvents are chosen as the catalysts. Highpurity graphite powder (99.99%, purity) is selected as a carbon source. The effects of cooling process on the qualities of Gem-diamond single crystals are studied carefully. First, in order to study the common crack defects of diamond single crystals, using scanning electron microscope (SEM), the surface morphologies of high quality diamond single crystals and crack crystals are obtained respectively. Our SEM test results show that the surfaces of the crack crystals and the high quality crystals are all very smooth. Therefore, the crack crystal problem is not directly caused by the unordered accumulation of carbon. Second, the concentrations of nitrogen in the high quality diamonds and crack crystals are measured by Fourier transform infrared. In our studies, the nitrogen content of the diamond single crystal with crack is similar to the nitrogen content of high quality single crystal, so the appearance of crystal crack is not caused by high impurity content. According to the test results and the regularity of the occurrence of crack crystals, the reasons for the occurrence of crack crystals are analyzed seriously. When the weather conditions such as seasonal change, wind, rain or snowfall are not very stable, the probability of crack crystal problem to appear will increase greatly. In our opinion, the decrease of diamond crystal quality caused by the fluctuation of external growth conditions is the internal cause of crack crystal problem appearing. After growing diamond crystals, choosing the traditional power failure mode and slowing cooling process respectively, the effect of cooling process on the quality of diamond single crystal is investigated. In the season of the crack problem occurring frequently, choosing power failure cooling process, cracks appear in both diamond crystals with 1.3 mm or 6.0 mm in diameter. With the slow cooling process, the synthetic diamond crystals with 1.2 mm or 5.8 mm in diameter are all high-quality single crystals with no cracks inside. The research results show that the slow cooling process can effectively restrain the occurrence of crack crystal problems. In addition, the mechanism problems of crack crystals and the mechanisms of the effects of slow cooling process on diamond crystal qualities are discussed in detail. We believe that the slow cooling process is effective in solving the crack crystal problem, which is mainly attributed to the following two aspects:on the one hand, the slow cooling makes the internal stress of diamond single crystal growing effectively released, which improves the compressive strength of the crystal and the crystal quality as well; on the other hand, the slow cooling makes the solidification process of the catalyst melt slowly, which provides enough time for the crystal to balance the external stress of the catalyst and the equipment, so that the crystals, which are not affected by the unbalanced external stress, are not cracked.

Shape controlled growth for type Ib large diamond crystals

The shape controlled growth of diamond is beneficial to its subsequent processing. The shape controlled growth for abrasive grade diamond, whose particle size is less than 1 mm, has been studied extensively, while the shape controlled growth of large diamond crystals, which have important commercial and scientific applications, has not been investigated in detail. Therefore, it is necessary to do further researches. In this study, we synthesize large type Ib diamond crystals and investigate their growth shapes at pressures of 5.3-5.9 GPa and temperatures of 1200-1370℃, by using Fe64Ni36 alloy as the catalyst and (100) or (111) face of seed as growth face. Experimental results show that for the diamond crystals grown along the (100) face, the crystal shapes presents plate shape at 1206-1215℃, tower shape at 1216-1260℃, and tower steeple shape at 1261-1360℃; in sequence while for those grown along the (111) face, the crystal shape is of tower at 1233-1238℃ and becomes plate at 1239-1364℃. The ratio of height to diameter, which can provide a standard to quantify the shape of a diamond, is used to describe the crystal shape in detail. For large diamond crystals growing along the (100) face, under a high pressure of 5.6 GPa, the ratio of height to diameter increases with temperature increasing but the ratio of height to diameter, when growing along the (111) face, decreases. The shape distributions of large diamond crystals in the V-shaped region can be determined in the experiments of large diamond crystal synthesis at different temperatures (1200-1370℃) and pressures (5.3 GPa, 5.6 GPa, 5.9 GPa). The lower limit temperature of large diamond crystal growing along the (111) face in the V-shape region is obviously higher than that growing along the (100) face, but the difference between the higher limit temperatures for growing along these two faces is not obvious. The difference between the lower temperature limits of large diamond crystals growing along the (100) and (111) face can be explained by the different energies of the crystal surface and diamond/graphite equilibrium line in the phase diagram of carbon/alloy. Therefore, it has been realized that the shapes for type Ib large diamond crystals are controlled.

Determination of Dose-Equivalent Response of A Typical Diamond Microdosimeter in Space Radiation Fields

Introduction: Microdosimeters are helpful for dose equivalent measurement in unknown radiation fields. The favorable physical and mechanical properties of the detector-grade chemical vapor deposition diamond materials have made the diamond microdosimeters suitable candidate for radioprotection applications in space. The purpose of this work is the investigation of the dose equivalent response of a typical diamond microdosimeter with laser-induced graphitized electrodes for use in space radiation fields. Materials and Methods: The Geant4 Monte Carlo simulation toolkit was applied to simulate the particle transport within the microdosimeter, and to determine the mean chord length and the dose equivalent response of the microdosimeter, based on the lineal energy dependent quality factor. Results: The linear stopping power of the protons and alpha particles with energies higher than 5 MeV and 10 MeV respectively can be estimated within20% of deviation using the microdosimeter response. The fluence to dose equivalent conversion coefficients calculated affirms that there is an adequate agreement between the calculated coefficients and other research group results. Conclusion: The reasonable agreement between the dose equivalents calculated in this study and the results reported by other researchers confirmed that this type of microdosimeter could be a promising candidate suitable for the measurement of the dose equivalent in space radiation fields.

Vickers Hardness of Diamond and cBN Single Crystals: AFM Approach

Atomic force microscopy in different operation modes (topography, derivative topography, and phase contrast) was used to obtain 3D images of Vickers indents on the surface of diamond and cBN single crystals with high spatial resolution. Confocal Raman spectroscopy and Kelvin probe force microscopy were used to study the structure of the material in the indents. It was found that Vickers indents in diamond has no sharp and clear borders. However, the phase contrast operation mode of the AFM reveals a new viscoelastic phase in the indent in diamond. Raman spectroscopy and Kelvin probe force microscopy revealed that the new phase in the indent is disordered graphite, which was formed due to the pressure-induced phase transformation in the diamond during the hardness test. The projected contact area of the graphite layer in the indent allows us to measure the Vickers hardness of type-Ib synthetic diamond. In contrast to diamond, very high plasticity was observed for 0.5 N load indents on the (001) cBN single crystal face. Radial and ring cracks were absent, the shape of the indents was close to a square, and there were linear details in the indent, which looked like slip lines. The Vickers hardness of the (111) synthetic diamond and (111) and (001) cBN single crystals were determined using the AFM images and with account for the elastic deformation of the diamond Vickers indenter during the tests.

Dependence of high density nitrogen-vacancy center ensemble coherence on electron irradiation doses and annealing time

Negatively charged nitrogen-vacancy (NV−) center ensembles in diamond have proved to have great potential for use in highly sensitive, small-package solid-state quantum sensors. One way to improve sensitivity is to produce a high-density NV− center ensemble on a large scale with a long coherence lifetime. In this work, the NV− center ensemble is prepared in type-Ib diamond using high energy electron irradiation and annealing, and the transverse relaxation time of the ensemble—T2—was systematically investigated as a function of the irradiation electron dose and annealing time. Dynamical decoupling sequences were used to characterize T2. To overcome the problem of low signal-to-noise ratio in T2 measurement, a coupled strip lines waveguide was used to synchronously manipulate NV− centers along three directions to improve fluorescence signal contrast. Finally, NV− center ensembles with a high concentration of roughly 1015 mm−3 were manipulated within a ~10 µs coherence time. By applying a multi-coupled strip-lines waveguide to improve the effective volume of the diamond, a sub-femtotesla sensitivity for AC field magnetometry can be achieved. The long-coherence high-density large-scale NV− center ensemble in diamond means that types of room-temperature micro-sized solid-state quantum sensors with ultra-high sensitivity can be further developed in the near future.

Effects of S on the synthesis of type Ib diamond under high pressure and high temperature

In this study, single crystal diamonds were successfully synthesized in a FeNi-S-C system under the constant conditions of 5.5GPa and 1400°C. The growth rate of the diamonds decreased due to the existence of sulfur (S) in the synthesis system. The color of the diamonds changed from yellow to light yellow with an increase in the S content. Compared to common type Ib diamonds synthesized in a FeNi-C system, the nitrogen concentration was higher in the synthesized diamonds when 0.1wt% S was added but was lower when the amount of S was increased to 0.25wt%. Raman measurements indicated that the use of S had almost no effect on the diamond lattice structure, thus diamond crystals with a high-quality sp3 structure were obtained. The photoluminescence (PL) spectra showed that the nitrogen-vacancy (NV) center occurred more likely in diamond lattice growth along the {111} face. Compared to the NV− center, the NV0 center could not be easily generated in the type Ib diamond lattice without the addition of S. Even if the NV0 and NV− centers were generated simultaneously in the diamond lattice with the addition of 0.25wt% S, the intensity was higher for the NV− peak than for the NV0 peak. The results of this study improve our understanding of the formation mechanisms of natural diamonds and represent an effective method for controlling the NV center in the diamond lattice.

Nano- and micron-sized diamond genesis in nature: An overview

There are four main types of natural diamonds and related formation processes. The first type comprises the interstellar nanodiamond particles. The second group includes crustal nano- and micron-scale diamonds associated with coals, sediments and metamorphic rocks. The third one includes nanodiamonds and microndiamonds associated with secondary alteration and replacing of mafic and ultramafic rocks. The fourth one includes macro-, micron- and nano-sized mantle diamonds which are associated with kimberlites, mantle peridotites and eclogites. Each diamond type has its specific characteristics. Nano-sized diamond particles of lowest nanometers in size crystallize from abiotic organic matter at lower pressures and temperatures in space during the stages of protoplanetary disk formation. Nano-sized diamonds are formed from organic matter at P-T exceeding conditions of catagenesis stage of lithogenesis. Micron-sized diamonds are formed from fluids at P-T exceeding supercritical water stability. Macrosized diamonds are formed from metal-carbon and silicate-carbonate melts and fluids at P-T exceeding 1150 °C and 4.5 GPa. Nitrogen and hydrocarbons play an important role in diamond formation. Their role in the formation processes increases from macro-sized to nano-sized diamond particles. Introduction of nitrogen atoms into the diamond structure leads to the stabilization of micron- and nano-sized diamonds in the field of graphite stability.

Evaluation of boron-doped-microcrystalline/nanocrystalline diamond composite coatings in drilling of CFRP

The drilling performance of four typical types of single-layer diamond coated drills and two-layer boron-doped-microcrystalline/nanocrystalline diamond (BDMC-NCD) composite coated drill is compared, and the growth duration ratio of the NCD layer to the BDMCD layer (N/B) is optimized. It is demonstrated that the BDMC-NCD film synthesized using proper N/B shows nice adhesion, moderate diamond quality and a smooth surface mostly composed of nano-sized diamond grains, so it shows the best comprehensive performance, including the thrust force reduction, the improvement of the hole quality, the slowing of the tool wear and coating peeling, and the elongation of the tool lifetime. Taking the time of the coating peeling into consideration, 3/9 is the optimum N/B for the BDMC-NCD coated drill, and such the drill also performs the longest lifetime using delamination factors (Fd) of 1.2 or 1.3 as the failure criteria. Moreover, the failure mode of the diamond coated drill is the flank wear when using Fd=1.1 or 1.2 as the failure criteria, while the tool failure should be related to the coating peeling when Fd=1.3.

Simulation Research on Micro Contact Based on Force in Silicon Wafer Rotation Grinding

Silicon wafer rotation grinding with cup type diamond wheel is a typical ultra precision grinding process. In this paper, a simulation model based on force for micro contact between wheel micro unit and silicon wafer is established from the stable ductile grinding process. Micro contact process in grinding is simulated using the nonlinear explicit finite element analysis software LS-DYNA. The stress-strain results on silicon wafer and wheel micro unit are analyzed by finite element method. The results show that the critical displacement and load corresponding elastic to plastic - plastic to brittle exist on silicon wafer. In silicon plastic zone tangential sliding can produce plastic groove and uplift. Wear of wheel micro unit can be based on the simulation data to judge. The research provides support for wafer grinding and wheel wear mechanism.

Laser Irradiation Responses of a Single-Crystal Diamond Produced by Different Crystal Growth Methods

Responses of two types of single-crystal diamonds, prepared by chemical vapour deposition (CVD) and high pressure high temperature synthesis (HPHT) methods, respectively, to a nanosecond pulsed neodymium-doped yttrium aluminium garnet (Nd:YAG) laser were investigated and compared. It was found that due to the difference in the transmission rate and refractive index, the laser-induced surface/subsurface features of the two types of samples were distinctly different. For the CVD sample, destructive interference takes place on the upper surface, leading to direct ablation of smooth grooves with deposition of graphite. For the HPHT sample, however, laser-induced grooves were formed on the reverse side of the irradiation surface (namely, the lower surface) at certain laser fluences due to the constructive interference phenomenon of the laser and the high refractive index of the material. The reverse-side irradiation resulted in the formation of deep and sharp grooves with rough bottoms and insignificant deposition of graphite on the area surrounding the groove. The machining thresholds for the upper and lower surfaces of both types of diamonds were experimentally obtained and theoretically verified. The findings of this study provide important process criteria for laser machining of different kinds of diamonds. The reverse-side irradiation method enables efficient machining of deep grooves in diamonds using a lower power laser.

Horn Fragments of the Halpern-Shoham Interval Temporal Logic

We investigate the satisfiability problem for Horn fragments of the Halpern-Shoham interval temporal logic depending on the type (box or diamond) of the interval modal operators, the type of the underlying linear order (discrete or dense), and the type of semantics for the interval relations (reflexive or irreflexive). For example, we show that satisfiability of Horn formulas with diamonds is undecidable for any type of linear orders and semantics. On the contrary, satisfiability of Horn formulas with boxes is tractable over both discrete and dense orders under the reflexive semantics and over dense orders under the irreflexive semantics but becomes undecidable over discrete orders under the irreflexive semantics. Satisfiability of binary Horn formulas with both boxes and diamonds is always undecidable under the irreflexive semantics.

Thick CVD diamond films grown on high-quality type IIa HPHT diamond substrates from New Diamond Technology

The suitability of type IIa diamonds prepared by High Pressure High Temperature (HPHT) in cubic presses at New Diamond Technology was assessed as substrates for the growth of thick detector-grade quality Chemically Vapour Deposited (CVD) diamond films. The substrates were found to possess a moderate dislocation density of about 103cm−2 and a reduced amount of residual impurities as compared to standard type Ib crystals. Using these diamonds as seeds for homoepitaxial growth, CVD films with improved structural characteristics were obtained although extended defects could not be completely prevented from forming and propagating. Their performance as detectors for β radiation was however improved leading to almost full charge collection which shows significant improvement as compared to CVD films grown under the same conditions on standard Ib HPHT diamonds. The availability of this new material source opens the way to the fabrication of higher quality CVD material for electronics applications.

LPHT annealing of brown-to-yellow type Ia diamonds

Low-pressure, high-temperature (LPHT) annealing of yellow-to-brown type Ia natural diamonds was performed to monitor its effects on optical centers within diamond, changes in the observed color, and to assess the process's viability as a commercial gem treatment.With LPHT annealing only, the mostly brown diamonds showed a shift towards yellow coloration; Vis-NIR absorption spectra showed this change was due to a modest increase in H3 intensity. Even at long annealing times (24h at 1800°C) or annealing at high temperatures (2000°C for five minutes), the diamonds did not significantly lose brown coloration. LPHT annealing showed itself as an ineffective means to break apart the vacancy clusters causing the brown color or causing nitrogen disaggregation, which resulted in only a small H3 generation.With LPHT annealing, “amber centers”—a group of several independent bands in the IR between 4200 and 4000cm−1 that disappear with HPHT annealing—were seen to anneal out gradually at various temperatures from 1700 to 2000°C.In contrast, high-pressure, high-temperature (HPHT) annealing effectively removes brown color at similar time/temperature conditions. Without the high stabilizing pressure provided by HPHT annealing techniques, the LPHT annealing showed pronounced damage on inclusions and dramatic surface etching.In subsequent experiments, LPHT annealing was used as a follow-up to laboratory irradiation. The irradiation-related vacancies created greater concentrations of H3 and the vacancy-assisted disaggregation of nitrogen created donors which led to a high concentration of H2 centers. This combination of defects resulted in a pronounced and favorable shift towards saleable yellow colors due to an increase in H3 and a dramatic increase in the H2 center, which led to the suppression of the remaining brownish component.The annealing characteristics for many centers detected by Vis-NIR absorption spectroscopy, FTIR absorption spectroscopy, and photoluminescence spectroscopy were chronicled throughout the study and compared with other LPHT annealing studies and HPHT annealing experiments.

Calculation of the temperature distribution at the HPHT growing of diamond single crystals in cells with two growth layers

Finite element method was used to calculate the distribution of temperatures in growth cells of the toroid TC-40 -type HPA. The experimental investigations of the process of growing type IIa diamond single crystals were performed in high-pressure cells with two growth layers. It is shown that in using the cell materials having appropriate properties and defined configuration of the system of the resistive heating the temperature gradients are 5.4–5.6°C/mm and the growth rate is 2.46 mg/h. The total weight of obtained structurally perfect type IIa diamond single crystals in the upper and lower growth layers is 1.18 and 1.13 carats, respectively, the nitrogen content in all grown crystals is 1–3 ppt.

Annealing and lateral migration of defects in IIa diamond created by near-threshold electron irradiation

The migration of vacancies in diamond is of considerable fundamental interest and has been widely studied previously, while the involvement of self-interstitials in diamond is less common except through centers such as 3H, 515.8 nm, 533.5 nm, and 580 nm. In this paper, the annealing and lateral migration of some interstitial-related centers in type IIa diamond are investigated by low temperature photoluminescence (PL) microscopy, and the distributions of interstitial- and vacancy-related centers are also clearly presented and discussed.

Anomalous lattice compressibility of hexagonal Eu2O3

Monoclinic Eu2O3 was investigated in a Mao-Bell type diamond anvil cell using angle dispersive x-ray diffraction up to a pressure of 26 GPa. Pressure induced structural phase transition from monoclinic to hexagonal phase was observed at 4.3 GPa with 2% volume collapse. Birch –Murnaghan equation of state fit to the pressure volume data yielded a bulk modulus of 159(9) GPa and 165(6) GPa for the monoclinic and hexagonal phases respectively. Equation of state fitting to the structural parameters yielded an axial compressibility of βa > βc > βb for the parent monoclinic phase, showing the least compressibility along b axis. Contrary to the available reports, an anomalous lattice compressibility behavior is observed for the high pressure hexagonal phase, characterized by pronounced hardening of a axis above 15 GPa. The observed incompressible nature of the hexagonal a axis in the pressure range 15–25 GPa is found to be compensated by doubling the compressibility along the c axis.

Synthesis and characterization of IIa-type S-doped diamond in FeNi catalyst under high pressure and high temperature conditions

In this work, service through nitrogen getter we have successfully synthesized sulfur(S) doped IIa-type diamond single crystals at 1400°C and 5.5GPa in FeNi-C system. We found that the synthetic diamond are mainly composited of the {111} faces because of the addition of S in the synthesis system. In addition, the color of our produced diamond changed from white to light brown and the shape of diamond changed from Cub-Octahedron to Octahedron with increase of S addition in the FeNi-C system. Furthermore, we notice that many kinds of defects, such as stratiform defects, craters and inverted pyramid defects appeared on the surfaces of diamonds induced by the additive of S. The FTIR results show that the obtained diamond crystals are IIa-type diamonds, containing less than 1ppm nitrogen. XPS measurement indicates that S was successfully incorporated into our produced diamond lattice in the SC and CSO forms. Raman spectra reveal that the as-growth S-doped IIa-type diamond single crystals possess a high-quality sp3 structure. Photoluminescence (PL) spectra demonstrate that nitrogen-vacancy is formed during diamond growth. Our work also helpful for understanding the formation of nature diamond.

A novel and simple x-ray slit for diamond anvil cell based x-ray diffraction experiments

We report here a novel internal x-ray slit assembly to carry out laboratory based high pressure x-ray diffraction (HPXRD) experiments in a Mao Bell type diamond anvil cell. In this assembly a tiny sheet of lead with a 100 micron hole immediately below the diamond table acts as an x-ray slit. Data resolution and statistics were compared with the older slit. This novel slit assembly has two major advantages (i) eliminates cumbersome and lengthy procedure usually adopted for alignment of x-ray slit (ii) provides high flux and improved resolution due to the comparatively low beam divergence and effective utilization of the maxima of the beam profile.

The relationship between platelet size and the B′ infrared peak of natural diamonds revisited

Platelets in diamond are extended planar defects that are thought to be generated during the nitrogen aggregation process in type Ia diamonds. They were subjected to intensive research during the 1980s and 1990s but the techniques used for observation of defects in diamond have improved since that time and new insights can be gained by further study. This study combines high resolution Fourier Transform Infrared (FTIR) analysis, with an emphasis on the main platelet peak, and transmission electron microscopic (TEM) imaging. By performing TEM and FTIR analyses on volumes of diamond that were closely spatially related it is shown that the average platelet diameter, D, follows the relationship D=ax−b where x is the position of the platelet peak in the infrared spectrum, a is a constant and b is the minimum position of the platelet peak. The best fit to the data is obtained if a value of b=1360cm−1 is used, giving a fitted value of a=221. The observed variation in infrared (IR) peak width can also be explained in terms of this relationship. Additionally, platelet morphology was found to vary according to diameter with large platelets being more elongated. The tendency to become more elongated can be described by the empirical equation AR=11.9D+19.6+0.4 where AR is the aspect ratio. Using the relationships established here, it will be possible to study platelet abundance and size as a function of parameters such as nitrogen concentration, nitrogen aggregation and diamond residence time in the mantle. This work therefore will open up new methods for constraining the geological history of diamonds of different parageneses and from different localities.