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physica status solidi (a)

Single‐Photon Emitters Based on Ge‐V Centers in Nanoparticles Obtained From CVD‐Grown Nanocrystalline Diamond Films

Ivan A. Tiazhelov, Мартьянов Артём Константинович, Alexey F. Popovich, Sergey S. Savin, Dmitrii G. Pasternak, Alexey M. Romshin, Alexander A. Zhivopistsev, Victoria Tapero, Pavel Aleksandrovich Pivovarov, Vadim Sedov

Published Sep 20, 2026• 0 citations
Publisher

Abstract

A method for obtaining luminescent diamond nanoparticles doped with germanium from nanocrystalline diamond (NCD) films grown by microwave plasma‐assisted chemical vapor deposition (MPCVD) is presented. Thermal etching in the presence of an alkali metal nitrate enables the selective disruption of intercrystallite boundaries, resulting in the formation of individual particles without mechanical grinding. Structural and morphological characterization by scanning and transmission electron microscopy, atomic force microscopy, Raman spectroscopy, and dynamic light scattering reveals the formation of particles with characteristic sizes down to ~100 nm, along with a minor fraction of larger microcrystals. The particles retain the crystalline quality of the parent film and exhibit photoluminescence associated with Ge‐V and Si‐V centers. Second‐order correlation measurements reveal single‐photon emission from a minority of Ge‐V‐related diffraction‐limited spots, demonstrating the presence of isolated optically active Ge‐V emitters in the nanoparticle sample. The proposed approach provides a scalable route for producing luminescent diamond nanoparticles for photonic and quantum applications.

DOI
10.1002/pssa.70538

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•Oct 30, 2025•0 citations
A method for obtaining luminescent diamond nanoparticles doped with germanium from nanocrystalline diamond (NCD) films grown by microwave plasma‐assisted chemical vapor deposition (MPCVD) is presented. Thermal etching in the presence of an alkali metal nitrate enables the selective disruption of intercrystallite boundaries, resulting in the formation of individual particles without mechanical grinding. Structural and morphological characterization by scanning and transmission electron microscopy, atomic force microscopy, Raman spectroscopy, and dynamic light scattering reveals the formation of particles with characteristic sizes down to ~100 nm, along with a minor fraction of larger microcrystals. The particles retain the crystalline quality of the parent film and exhibit photoluminescence associated with Ge‐V and Si‐V centers. Second‐order correlation measurements reveal single‐photon emission from a minority of Ge‐V‐related diffraction‐limited spots, demonstrating the presence of isolated optically active Ge‐V emitters in the nanoparticle sample. The proposed approach provides a scalable route for producing luminescent diamond nanoparticles for photonic and quantum applications.
Diamond nanoparticles with optically active color centers can be used in nanoscale devices for quantum networking and sensing. A particular interest is focused on nanodiamonds (NDs) containing a small ensemble of negatively charged silicon‐vacancy (SiV) centers. Such NDs can be integrated with on‐chip optical structures. Here, chemical vapor deposition (CVD) is used to synthesize diamond particles of less than 100 nm in size containing 10–20 centers per ND. Two types of NDs grown on a Si substrate are studied, seeded with detonation NDs and without any seeding. The SiV luminescence under off‐resonant and resonant laser excitation at the temperature of 15 K is investigated. The emission lines of SiVs of individual NDs are well resolved and found to be spread in the range of 730–750 nm. The typical SiV linewidth is within 1–2 GHz for spontaneous NDs, which is only a factor of 2.5–5 broader than the lifetime limited linewidth of the SiV at 15 K. The emission of a single SiV is highly stable for both types of samples. This work is a critical step toward the synthesis of SiVs suitable for the realization of integrated quantum photonic devices.
Point defects in diamond, promising candidates for nanoscale pressure- and temperature-sensing applications, are potentially scalable in polycrystalline diamond fabricated using the microwave plasma-enhanced chemical vapor deposition (MW PE CVD) technique. However, this approach introduces residual stress in the diamond films, leading to variations in the characteristic zero phonon line (ZPL) of the point defect in diamond. Here, we report the effect of residual stress on germanium-vacancy (GeV) centers in MW PE CVD nanocrystalline diamond (NCD) films fabricated using single crystal Ge as the substrate and solid dopant source. GeV ensemble formation indicated by the zero phonon line (ZPL) at ∼602 nm is confirmed by room temperature (RT) photoluminescence (PL) measurements. PL mapping results show spatial nonuniformity in GeV formation along with other defects, including silicon-vacancy centers in the diamond films. The residual stress in NCD results in shifts in the PL peak positions. By estimating a stress shift coefficient of (2.9 ± 0.9) nm/GPa, the GeV PL peak position in the NCD film is determined to be between 598.7 and 603.2 nm. A larger ground state splitting due to the strain on a GeV-incorporated NCD pillar at a low temperature (10 K) is also reported. We also report the observation of intense ZPLs at RT that in some cases could be related to low Ge concentration and the surrounding crystalline environment. In addition, we also observe thicker microcrystalline diamond (MCD) films delaminate from the Ge substrate due to film residual stress and graphitic phase at the diamond/Ge substrate interface (confirmed by electron energy loss spectroscopy). Using this approach, a free-standing color center incorporated MCD film with dimensions up to 1 × 1 cm 2 is fabricated. Qualitative analysis using time-of-flight secondary ion mass spectroscopy reveals the presence of impurities, including Ge and silicon, in the MCD film. Our experimental results will provide insights into the scalability of GeV fabrication using the MW PE CVD technique and effectively implement NCD-based nanoscale-sensing applications.
Fluorescent emitters in diamond are considered to be a valuable resource for fields such as quantum communication, quantum photonics, and biological imaging. In this paper, we report a wide range of narrow bandwidth ( ~ 1.5 nm) spectral emission lines arising from different color centers at room temperature. The defects were created by chemical vapor deposition of thin diamond films grown on silica substrates seeded with nanoparticles of diamond and nickel. These fluorescent lines also possess single or few centers photon statistics. We correlate the zero-phonon lines, observed using confocal microscopy, with previously identified nickel-related centers which have been observed in high-pressure high-temperature diamond, with a Si/Ni complex and silicon vacancy defects. We compare our findings with recent results demonstrating single-photon emission in diamond associated with nickel-related centers to clarify and summarize previous studies concerning this specific dopant. The great variety of emission lines observed in the synthesized material, mainly associated with nickel-related centers, could be an important resource for applications relying on the presence of several emitters of single photons in the same sample. Moreover, the possibility of mass production of these centers in nanodiamonds in colloidal suspension may provide an important resource for biomarking and microscopy.
Group IV color centers in diamond (Si, Ge, Sn, and Pb) have recently emerged as promising candidates for realization of scalable quantum photonics. However, their synthesis in nanoscale diamond is still in its infancy. In this work we demonstrate controlled synthesis of selected group IV defects (Ge and Sn) into nanodiamonds and nanoscale single crystal diamond membranes by microwave plasma chemical vapor deposition. We take advantage of inorganic salts to prepare the chemical precursors that contain the required ions that are then incorporated into the growing diamond. Photoluminescence measurements confirm that the selected group IV emitters are present in the diamond without degrading its structural quality. Our results are important to expand the versatile synthesis of color centers in diamond.
We report on the high-pressure synthesis of novel nano- and microcrystalline diamonds with germanium–vacancy (Ge–V) color centers emitting at 602 nm. The synthesis was carried out in non-metallic growth systems C–H–Ge and C–H–O–Ge enriched with germanium and carbon isotopes. We demonstrate germanium and carbon isotope shifts in the fine structure of the luminescence, which allows us to unambiguously associate the center with the germanium impurity entering into the diamond lattice. We show that there are two ground-state energy levels with the separation of 0.7 meV and two excited-state levels separated by 4.6 meV in the electronic structure of the center and suggest a split-vacancy structure of this center. High-intensity and narrow-line emission of high-pressure synthesized small diamonds with Ge–V centers makes them promising candidates for single-photon emitters.
Progress in controlling diamond synthesis has made it possible to produce very pure crystals and to incorporate and control atomic impurities and carbon vacancies in the crystal lattice. The appropriate impurity-vacancy combinations can give rise to special defects known as color centers, such as the nitrogen-vacancy (NV) or the silicon-vacancy (SiV), which exhibit exceptional quantum properties with spins that are optically addressable. The use of diamond containing color centers has paved the way for the development of innovative quantum technologies, such as very high-resolution magnetometry and quantum information processing. Nevertheless, the development of quantum sensors at the nanometric scale remains one of the most interesting challenges. In this context, the development of a reliable nanoparticle synthesis technique that allows the desired defects to be incorporated and their quantum optical properties to be modulated is crucial. In this seminar, an efficient and recent method to produce diamond nanoparticles containing NV, SiV and germanium-vacancy (GeV) centers is proposed through direct plasma assisted chemical vapour deposition (CVD) growth. This technique allows good control of both nanoparticle growth processes and color centers formation. The optimization of the CVD nanodiamond growth process is presented, showing the impact of different plasma parameters and gas phasecomposition on nanoparticle crystallinity, size and shape. Morphological characterizations reveal the production of small (around 100 nm) and well faceted nanodiamond particles. In addition, the SiV and GeV color centers incorporation can be tuned within this material by varying the gas phase composition which emphasizes the high flexibility of the CVD growth technique. Finally, the quantum properties of the incorporated color centers have been successfully investigated under extreme pressure conditions (up to ~ 180 GPa) showing a monotonic blue shift of their optical zero-phonon line. Since their luminescence remains stable, SiV and GeV centers emerge as high-pressure nanosensors.