Germanium-vacancy Centers Research Articles

A germanium-vacancy center in diamond as single-photon source for radiometric application

Abstract We present the metrological characterization of a single-photon source based on a germanium-vacancy center in diamond under a solid immersion lens in a confocal microscope setup at room temperature. It was characterized in terms of the emission’s spectral distribution, single-photon purity, temporal stability and the emitter’s excited state lifetime and saturation behavior. An Allan deviation analysis was performed on the emission of the single-photon source to determine the optimal averaging time of the photon flux. The single-photon source was used for the relative calibration of the detection efficiency of two single-photon avalanche diode detectors. The results were compared with measurements using attenuated laser light for the calibration of the detectors.

Lifetime Reduction of Single Germanium-Vacancy Centers in Diamond via a Tunable Open Microcavity

Coupling between a single quantum emitter and an optical cavity presents a key capability for future quantum networking applications. Here, we explore interactions between individual germanium-vacancy (GeV) defects in diamond and an open microcavity at cryogenic temperatures. Exploiting the tunability of our microcavity system to characterize and select emitters, we observe a Purcell-effect-induced lifetime reduction of up to 4.5±0.3 and extract coherent-coupling rates up to 360±20 MHz. Our results indicate that the GeV defect has favorable optical properties for cavity coupling, with a quantum efficiency of at least 0.34±0.05 and likely much higher. Published by the American Physical Society 2024

Structural formation yield of GeV centers from implanted Ge in diamond

In order to study the structural formation yield of germanium-vacancy (GeV) centers from implanted Ge in diamond, we have investigated its lattice location by using the β − emission channeling technique from the radioactive isotope 75Ge (t 1/2 = 83 min) produced at the ISOLDE/CERN facility. 75Ge was introduced via recoil implantation following 30 keV ion implantation of the precursor isotope 75Ga (126 s) with fluences around 2 × 1012–5 × 1013 cm−2. While for room temperature implantation fractions around 20% were observed in split-vacancy configuration and 45% substitutional Ge, following implantation or annealing up to 900 °C, the split-vacancy fraction dropped to 6%–9% and the substitutional fraction reached 85%–96%. GeV complexes thus show a lower structural formation yield than other impurities, with substitutional Ge being the dominant configuration. Moreover, annealing or high-temperature implantation seem to favor the formation of substitutional Ge over GeV. Our results strongly suggest that GeV complexes are thermally unstable and transformed to substitutional Ge by capture of mobile carbon interstitials, which is likely to contribute to the difficulties in achieving high formation yields of these optically active centers.

Annealing process and temperature effects on silicon-vacancy and germanium-vacancy centers in CVD grown polycrystalline diamond

The annealing treatment plays a crucial role in tailoring the properties of synthetic diamond materials, especially those doped with various elements in order to form specific color centers like nitrogen-vacancy (NV), silicon-vacancy (Si-V), germanium-vacancy (Ge-V), etc. This study delves into the annealing of 175 μm-thick Ge-doped polycrystalline diamond (PCD) films grown by microwave plasma-assisted chemical vapor deposition (MPCVD). Large-area PCD plate was cut into smaller equivalent 5 × 5 mm2 pieces, which were separately subjected to annealing in microwave plasma in H2 atmosphere, to annealing in vacuum or to annealing under high-pressure high-temperature conditions (HPHT, 5.9 GPa, 2000 °C). The structure, phase composition and photoluminescence (PL) of samples before and after various annealing processes were investigated. All applied types of annealing enhance both the Si-V and Ge-V lines in PL at room temperature. Increasing annealing temperature leads to gradual decrease of full widths at half-maxima (FWHM) of diamond Raman peak (1332.5 cm−1), as well as Si-V (738 nm) and Ge-V (602 nm) PL peaks. In addition, the limitations for each type of annealing are established. The obtained results are crucial for the design of CVD-grown Ge-doped and Si-doped PCD materials that can be used for applications in photonics such as single photon sources, biomarkers, as well as for the fabrication of optical diamond thermometers.

Optical properties of negatively charged germanium-vacancy centers in detonation nanodiamonds with an average single-digit nanometer particle size

Nanodiamonds that contain germanium-vacancy centers (GeV-NDs) exhibit significant potential for biomedical and quantum science applications. GeV-NDs with an average particle size of 9 nm were recently fabricated through a detonation process that enables the practical-scale production of detonation NDs (DNDs). However, the optical properties of the GeV centers in the DNDs have not been studied thoroughly. In particular, the luminescence spectrum of these GeV-DNDs had an unassigned peak at 1.98 eV. Here, we investigate the optical properties of GeV-DNDs under various conditions. Although the GeV-DNDs exhibit a zero-phonon line (ZPL) with similar excitation energy dependence and photostability to their bulk counterparts, the ZPL linewidth is broader. The 1.98 eV-peak is attributed to a composite phonon sideband peak. The unique properties of the GeV centers in these small DNDs are explained by enhanced electron–phonon coupling.

The luminescence study of GeV centers and damage in diamond induced by 300keV Ge ion implantation

In this paper, the germanium-vacancy (GeV) in diamond produced by 300 keV Ge ion implantation and subsequent annealing, were investigated by Raman spectroscopy and photoluminescence (PL) spectroscopy, and meanwhile the different ion injection models were given by the Stopping and the Rang of Ions in Matter (SRIM) simulation. Results showed that the Raman peak of diamond shifted to the lower wavenumber after Ge ion implantation, indicating the ion implantation caused amorphous graphitization in the crystal that generated the local tensile stress. Most of the amorphous graphitization was eliminated at an annealing temperature of 300–700 °C by evidence of the variation of ID/IG value. When the annealing temperature was higher than 700 °C, the vacancy migrate a longer distance to find Ge ions, then convert Ge ions into GeV centers, and thus an interesting zero phonon line (ZPL) at 602.8 nm appeared which was associated with GeV center.

Germanium-vacancy centers in detonation nanodiamond for all-optical nanoscale thermometry

Nanodiamonds with group-IV color centers, such as silicon-vacancy centers and germanium-vacancy (GeV) centers, exhibit excellent properties, including a sharp and stable zero-phonon line, surface functionalization, and low cytotoxicity. Because the line peak wavelength shifts linearly with the temperature under ambient conditions, the nanodiamonds are promising candidates for all-optical nanoscale thermometry inside a living cell. However, the particles used for temperature measurements have been reported to be larger than a few hundred nanometers. Here, we report temperature sensing using GeV detonation nanodiamonds. The GeV nanodiamonds have a mean particle size of 20 nm. These are the smallest particles among GeV-based particles used in thermometry. The sensitivity of the single GeV centers in the detonation nanodiamond is estimated to be almost consistent with the reported ones of the single GeV centers in bulk diamonds, which can potentially reach sub-kelvin temperature accuracy. The GeV detonation nanodiamonds should function as good photoluminescence probes and intracellular temperature sensors.

Formation of Ge-V color centers in poly- and monocrystalline CVD diamond: A comparative study

Germanium-Vacancy (Ge-V) color centers in diamond have narrow-band photoluminescence (PL) at room temperature (RT) and attract considerable attention due to their possible application in quantum information technologies, biomedicine, and local optical thermometry. In this work, we used microwave plasma chemical vapor deposition (MPCVD) to synthesize Ge-doped polycrystalline diamond (PCD) films and single-crystal diamond (SCD) epitaxial layers in hydrogen-methane-germane gas mixtures. Thick (>100 μm) layers of both types were grown to analyze their structure and luminescence characteristics. The first demonstration of the absorption of Ge-V centers in both PCD and SCD materials at low temperatures is presented. The sufficient narrowing of the Ge-V PL line for the SCD sample in comparison with the PCD sample was observed. On the other hand, the intensity of the Ge-V signal was an order of magnitude higher in the PCD sample compared to the SCD sample. A set of single Ge-V centers formed during CVD has been demonstrated. The results obtained can be used to manufacture and design various photonic devices based on Ge-V color centers.

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

AbstractThe 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.

Bright single-photon emission from a GeV center in diamond under a microfabricated solid immersion lens at room temperature

We report on the metrological characterization of the emission from a germanium-vacancy center in diamond under a microfabricated solid immersion lens in a confocal laser-scanning microscope setup. Ge ions were implanted into a synthetic diamond at 3 MeV, and germanium-vacancy centers were then formed by subsequent annealing. Afterward, solid immersion lenses were fabricated in a focused ion beam scanning electron microscope. The photoluminescence was investigated at room temperature in terms of the spectral distribution, the excited state lifetime, the second-order correlation function, and the saturation behavior, proving simultaneous high single-photon purity and high brightness. Two methods were exploited to minimize the residual multi-photon probability: spectral filtering and temporal filtering. According to these results, we assume that Raman scattered photons and emission from neighboring color centers play an important role in the residual multi-photon emission probability. The system efficiency of the single-photon source was investigated and found to be in accordance with the value calculated from all sources of loss in the setup. The branching ratio of the germanium-vacancy center for the decay into the ground state and into metastable state was calculated. The results enable the usage of the single-photon source in future quantum radiometric experiments.

In situ doping of epitaxial diamond with germanium by microwave plasma CVD in GeH4-CH4-H2 mixtures with optical emission spectroscopy monitoring.

We report the growth of Ge-doped homoepitaxial diamond films by microwave plasma CVD in GeH4-CH4-H2 gas mixtures at moderate pressures (70-100 Torr). Optical emission spectroscopy was used to monitor Ge, H, and C2 species in the plasma at different process parameters, and trends for intensities of those radicals, gas temperature, and excitation temperature, with variations of GeH4 or CH4 precursor concentrations, were investigated. The film deposited on (111)-oriented single crystal diamond substrates in a high growth rate regime revealed a strong emission of a germanium-vacancy (GeV) color center with a zero-phonon line at ≈604 nm wavelength in photoluminescence (PL) spectra, confirming the successful doping. The observed PL shift for the GeV defect is caused by stress in the films, as evidenced and quantified by Raman spectra. These results suggest that in situ doping with Ge using a GeH4 precursor is a convenient method of controlling the formation of GeV centers in epitaxial diamond films for photonic applications.

Direct synthesis of group IV-vacancy center-containing nanodiamonds via detonation process using aromatic compound as group IV element source

Nanodiamonds (NDs) containing group IV-vacancy (G4V) centers—silicon-vacancy (SiV), germanium-vacancy (GeV) and tin-vacancy (SnV) centers—have shown promising potential as fluorescent markers for bioimaging and -sensing. However, the scale of fabrication has been limited to the laboratory scale. In this study, a detonation process was applied that enables practical scale fabrication of NDs for the direct synthesis of these G4V center-containing NDs (G4V-NDs). This detonation process for the direct synthesis of G4V-NDs employed explosives with the addition of dopant molecules with group IV atoms centered on tetraphenyl compounds. The successful synthesis of negatively charged SiV and GeV center-containing NDs (SiV- and GeV-NDs) was evidenced by photoluminescence (PL) spectra with zero-phonon lines (ZPLs) attributed to such color centers. However, as a result of the same strategy, NDs containing the SnV centers were not obtained in detectable concentrations in PL measurements. When the generated concentrations of SiV- and GeV-NDs synthesized under identical conditions were evaluated based on the number of data points that clear ZPLs were observed on the PL mappings, the SiV-NDs were found to be produced more predominantly than the GeV-NDs. The physics behind such results is explained by the difference in the reaction thermodynamics for each group IV atom. • Detonation process (DP) enables practical scale production of nanodiamonds (NDs). • Direct synthesis of NDs containing SiV or GeV centers was achieved by DP. • As Si or Ge sources in DP, atoms centered on tetraphenyl compounds were used. • SnV centers were not detected in NDs obtained via same scheme. • This is due to the difference in the reaction thermodynamics for each heteroatom.

Unusual temperature dependence of the photoluminescence emission of MgV centers in diamond

Magnesium-and germanium-vacancy centers were produced in diamond by ion implantation and the post-annealing process. Photoluminescence spectroscopy (PL) measurements were performed between 20 and 50 °C. The PL results of the GeV centers are in agreement with those found in the literature, while the MgV center is newly discovered and a not yet broadly investigated color center, but the room temperature PL results are in agreement with the first report. The temperature dependence of the MgV centers above room temperature is unusual: by increasing the temperature, its PL shifts to higher energies, contrary to what is observed for the GeV centers and other known centers in the literature. The zero phonon line width of both centers broadens by increasing the temperature in both investigated centers. The origin of the blue shift observed in the MgV centers as a confinement effect is discarded, because sample is bulk and its origin should lay on the influence of the temperature on the local static structure and the overlapping of the electronic wave functions. Our results show the ability of MgV to be used in future for thermometry. The center is bright and photostable, with a narrow full width at half maximum compared to other centers in diamond and its shift with the temperature is also larger.

Localized vibrational modes of GeV-centers in diamond: Photoluminescence and first-principles phonon study

The vibrational behaviour of the germanium-vacancy (GeV) in diamond is studied through its photoluminescence spectrum and first-principles modelled partial phonon density of states. The former is measured in a region below 600 cm−1. The latter is calculated for the GeV center in its neutral, charged, and excited state. The photoluminescence spectrum presents a previously unobserved feature at 248 cm−1 in addition to the well-known peak at 365 cm−1. In our calculations, two localized modes, associated with the GeV center and six nearest carbon atoms (GeC6 cluster) are identified. These correspond to one vibration of the Ge ion along with the [111] orientation of the crystal and one perpendicular to this direction. We propose these modes to be assigned to the two features observed in the photoluminescence spectrum. The dependence of the energies of the localized modes on the GeV-center and their manifestation in experimental optical spectra is discussed.

Control of NV, SiV and GeV centers formation in single crystal diamond needles

Single-crystal diamond needles in the form of micrometer-scale sharp pyramids were produced using a combination of chemical vapor deposition and thermal oxidation processes. These diamond needles with atomic-sized fluorescent defects (color centers) attract great interest for practical applications as a platform for creation of optical quantum sensing probes and optical quantum communication elements. Particular color centers localization providing suitable luminescence characteristics is required for these applications. Here we report about formation of nitrogen-vacancy (NV), silicon-vacancy (SiV) and germanium-vacancy (GeV) centers in the single-crystal diamond needles during direct current discharge plasma enhanced chemical vapor deposition (PE CVD). Luminescent characteristics of the needles were observed by confocal photoluminescence mapping. Analysis of experimental results allows us proposing possible mechanisms of impurities introduction into the crystal lattice during needles growth. These mechanisms include gas decomposition and etching of substrate material during CVD. The proposed mechanisms were approved by realization of CVD process protocols resulting in controllable formation of NV, SiV and GeV centers in single-crystal diamond needles including formation of thin NV- and SiV- enriched layers by tuning deposition process parameters. The proposed experimental approaches in combination with revealed mechanisms for introduction of favorable impurities make single-crystal diamond needles promising candidates for scanning quantum sensing, quantum communication and hyperpolarization experiments.

Bottom‐Up Synthesis of Single Crystal Diamond Pyramids Containing Germanium Vacancy Centers

AbstractDiamond resonators containing color‐centers are highly sought after for application in quantum technologies. Bottom‐up approaches are promising for the generation of single‐crystal diamond structures with purposely introduced color centers. Here the possibility of using a polycrystalline diamond to grow single‐crystal diamond structures by employing a pattern growth method is demonstrated. For, the possible mechanism of growing a single‐crystal structure with predefined shape and size from a polycrystalline substrate by controlling the growth condition is clarified. Then, by introducing germanium impurities during the growth, localized and enhanced emission from fabricated pyramid shaped single‐crystal diamonds containing germanium vacancy (GeV) color centers is demonstrated. Finally, linewidth of ∼500 MHz at 4 K from a single GeV center in the pyramid shaped diamonds is measured. The method is an important step toward fabrication of 3D structures for integrated diamond photonics.

Fluorescence enhancement of a single germanium vacancy center in a nanodiamond by a plasmonic Bragg cavity.

Germanium vacancy (GeV) centers in diamonds constitute a promising platform for single-photon sources to be used in quantum information technologies. Emission from these color centers can be enhanced by utilizing a cavity that is resonant at the peak emission wavelength. We investigate circular plasmonic Bragg cavities for enhancing the emission from single GeV centers in nanodiamonds (NDs) at the zero phonon line. Following simulations of the enhancement for different configuration parameters, the appropriately designed Bragg cavities together with out-coupling gratings composed of hydrogen silsesquioxane ridges are fabricated around the NDs containing nitrogen vacancy centers deposited on a silica-coated silver surface. We characterize the fabricated configurations and finely tune the cavity parameters to match the GeV emission. Finally, we fabricate the cavity containing a single GeV-ND and compare the total decay-rate before and after cavity fabrication, finding a decay-rate enhancement of ∼5.5 and thereby experimentally confirming the feasibility of emission enhancement with circular plasmonic cavities.

Robust Detection of High-Frequency Signals at the Nanoscale

We present a method relying on shortcuts to adiabaticity to achieve quantum detection of high frequency signals at the nanoscale in a robust manner. More specifically, our protocol delivers tailored amplitudes and frequencies for control fields that, firstly, enable the coupling of the sensor with high-frequency signals and, secondly, minimise errors that would otherwise spoil the detection process. To exemplify the method, we particularise to detection of signals emitted by fast-rotating nuclear spins with nitrogen vacancy center quantum sensors. However, our protocol is straightforwardly applicable to other quantum devices such as silicon vacancy centers, germanium vacancy centers, or divacancies in silicon carbide.

Free-standing silicon nitride nanobeams with an efficient fiber-chip interface for cavity QED

We present the design, fabrication and characterization of high quality factor silicon nitride nanobeam PhC cavities at visible wavelengths for coupling to diamond color centers in a cavity QED system. We demonstrate devices with a quality factor of ∼24, 000 (±250) around the zero-phonon line of the germanium-vacancy center in diamond. We also present an efficient fiber-to-waveguide coupling platform for suspended nanophotonics. By gently changing the corresponding effective indices at the fiber-waveguide interface, we achieve a coupling efficiency of ∼96% (±2%) at the cavity resonance.

Optical manipulation of the negative silicon-vacancy center in diamond

The silicon-vacancy center in diamond has recently attracted significant attention as a candidate for quantum information processing as it overcomes many of the optical issues present in the nitrogen-vacancy center. Historically it has been hampered by short dephasing times; however the recent development of high-purity samples at low temperatures resolves this issue. Hence it is timely to explore whether silicon-vacancy centers are useful for quantum tasks beyond single-photon sources. Here we investigate the potential of the silicon-vacancy center to realize two important operations required for quantum information processing: high-efficiency projective measurement and efficient single-qubit rotations. Due to its similar nature, the germanium-vacancy center is discussed as a point of comparison.