Efficiency Optimization of Ge-V Quantum Emitters in Single-Crystal Diamond upon Ion Implantation and HPHT Annealing

The authors report on the characterization at the single-defect level of germanium-vacancy (GeV) centers in diamond produced upon Ge− ion implantation and different subsequent annealing processes, with a specific focus on the effect of high-pressure-high-temperature (HPHT) processing on their quantum-optical properties. Different post-implantation annealing conditions are explored for the optimal activation of GeV centers, namely, 900 °C 2 h, 1000 °C 10 h, 1500 °C 1 h under high vacuum, and 2000 °C 15 min at 6 GPa pressure. A systematic analysis of the relevant emission properties, including the emission intensity in saturation regime and the excited state radiative lifetime, is performed on the basis of a set of ion-implanted samples, with the scope of identifying the most suitable conditions for the creation of GeV centers with optimal quantum-optical emission properties. The main performance parameter adopted here to describe the excitation efficiency of GeV centers as single-photon emitters is the ratio between the saturation optical excitation power and the emission intensity at saturation. The results show an up to eightfold emission efficiency increase in HPHT-treated samples with respect to conventional annealing in vacuum conditions, suggesting a suitable thermodynamic pathway toward the repeatable fabrication of ultra-bright GeV centers for single-photon generation purposes

Effect of Rare-Earth Element Oxides on Diamond Crystallization in Mg-Based Systems

Diamond crystallization in Mg-R2O3-C systems (R = Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb) was studied at 7.8 GPa and 1800 °C. It was found that rare-earth oxide additives in an amount of 10 wt % did not significantly affect both the degree of graphite-to-diamond conversion and crystal morphology relative to the Mg-C system. The effect of higher amounts of rare-earth oxide additives on diamond crystallization was studied for a Mg-Sm2O3-C system with a Sm2O3 content varied from 0 to 50 wt %. It was established that with an increase in the Sm2O3 content in the growth system, the degree of graphite-to-diamond conversion decreased from 80% at 10% Sm2O3 to 0% at 40% Sm2O3. At high Sm2O3 contents (40 and 50 wt %), instead of diamond, mass crystallization of metastable graphite was established. The observed changes in the degree of the graphite-to-diamond conversion, the changeover of diamond crystallization to the crystallization of metastable graphite, and the changes in diamond crystal morphology with increasing the Sm2O3 content attested the inhibiting effect of rare-earth oxides on diamond crystallization processes in the Mg-Sm-O-C system. The crystallized diamonds were studied by a suite of optical spectroscopy techniques, and the major characteristics of their defect and impurity structures were revealed. For diamond crystals produced with 10 wt % and 20 wt % Sm2O3 additives, a specific photoluminescence signal comprising four groups of lines centered at approximately 580, 620, 670, and 725 nm was detected, which was tentatively assigned to emission characteristic of Sm3+ ions

Crystallization of Diamond from Melts of Europium Salts

Diamond crystallization in melts of europium salts (Eu2(C2O4)3·10H2O, Eu2(CO3)3·3H2O, EuCl3, EuF3, EuF2) at 7.8 GPa and in a temperature range of 1800–2000 °C was studied for the first time. Diamond growth on seed crystals was realized at a temperature of 2000 °C. Spontaneous diamond nucleation at these parameters was observed only in an Eu oxalate melt. The maximum growth rate in the europium oxalate melt was 22.5 μm/h on the {100} faces and 12.5 μm/h on the {111} faces. The diamond formation intensity in the tested systems was found to decrease in the following sequence: Eu2(C2O4)3·10H2O > Eu2(CO3)3·3H2O > EuF3 > EuF2 = EuCl3. Diamond crystallization occurred in the region of stable octahedral growth in melts of Eu3+ salts and in the region of cubo-octahedral growth in an EuF2 melt. The microrelief of faces was characterized by specific features, depending on the system composition and diamond growth rate. In parallel with diamond growth, the formation of metastable graphite in the form of independent crystals and inclusions in diamond was observed. From the spectroscopic characterization, it was found that diamonds synthesized from Eu oxalate contain relatively high concentrations of nitrogen (about 1000−1200 ppm) and show weak PL features due to inclusions of Eu-containing species

Experimental Modeling of Ankerite–Pyrite Interaction under Lithospheric Mantle P–T Parameters: Implications for Graphite Formation as a Result of Ankerite Sulfidation

Experimental modeling of ankerite–pyrite interaction was carried out on a multi-anvil high-pressure apparatus of a “split sphere” type (6.3 GPa, 1050–1550 °C, 20–60 h). At T ≤ 1250 °C, the formation of pyrrhotite, dolomite, magnesite, and metastable graphite was established. At higher temperatures, the generation of two immiscible melts (carbonate and sulfide ones), as well as graphite crystallization and diamond growth on seeds, occurred. It was established that the decrease in iron concentration in ankerite occurs by extraction of iron by sulfide and leads to the formation of pyrrhotite or sulfide melt, with corresponding ankerite breakdown into dolomite and magnesite. Further redox interaction of Ca,Mg,Fe carbonates with pyrrhotite (or between carbonate and sulfide melts) results in the carbonate reduction to C0 and metastable graphite formation (±diamond growth on seeds). It was established that the ankerite–pyrite interaction, which can occur in a downgoing slab, involves ankerite sulfidation that triggers further graphite-forming redox reactions and can be one of the scenarios of the elemental carbon formation under subduction settings

Synthetic single crystal diamonds for X-ray optics

In the manuscript we report on characterization of single-crystalline (111) plates prepared from type Ib diamonds with nitrogen content of 100-150 ppm and (100) plates prepared from IIa diamond by means of high-resolution rocking curve imaging (RCI). Contrary to a common opinion about intrinsic poor diffraction quality of type Ib diamonds, RCI showed the presence of nearly defect-free areas of several mm2 in the central part of the (111)-oriented diamond plates. In comparison with the (100)-oriented IIa diamond plates prepared by the same HPHT setup the Ib diamonds possess better diffraction quality. The observed broadening of the rocking curves associates with the cutting and polishing processes, causing strains around the edges of the plates and rare defects. An improvement of preparation technique will thus allow to make single-crystalline diamond plates for Laue and Bragg monochromators and beam splitters from type Ib diamond with areas large enough to be used as wavefront-preserving optical elements at 4th generation synchrotron facilities. Contrary to a common opinion about intrinsically poor diffraction quality of type I diamonds, RCI showed the presence of nearly defect-free areas of several mm2 in the central part of the diamond plates. The observed broadening of the rocking curves results from the cutting and polishing processes, causing strains around the edges of the plates and rare defects. An improvement of preparation technique will thus allow to make single-crystalline diamond plates for Laue and Bragg monochromators and beam splitters from type Ib material with areas large enough to be used as optical elements at 4th generation synchrotron facilities