Giant Quantum Electrodynamic Effects on Single SiV Color Centers in Nanosized Diamonds.

Understanding and mastering quantum electrodynamics phenomena is essential to the development of quantum nanophotonics applications. While tailoring of the local vacuum field has been widely used to tune the luminescence rate and directionality of a quantum emitter, its impact on their transition energies is barely investigated and exploited. Fluorescent defects in nanosized diamonds constitute an attractive nanophotonic platform to investigate the Lamb shift of an emitter embedded in a dielectric nanostructure with high refractive index. Using spectral and time-resolved optical spectroscopy of single SiV defects, we unveil blue shifts (up to 80 meV) of their emission lines, which are interpreted from model calculations as giant Lamb shifts. Moreover, evidence for a positive correlation between their fluorescence decay rates and emission line widths is observed, as a signature of modifications not only of the photonic local density of states but also of the phononic one, as the nanodiamond size is decreased. Correlative light-electron microscopy of single SiVs and their host nanodiamonds further supports these findings. These results make nanodiamond-SiVs promising as optically driven spin qubits and quantum light sources tunable through nanoscale tailoring of vacuum-field fluctuations.

Allotropic Ga2Se3/GaSe nanostructures grown by van der Waals epitaxy: narrow exciton lines and single-photon emission.

The ability to emit narrow exciton lines, preferably with a clearly defined polarization, is one of the key conditions for the use of nanostructures based on III-VI monochalcogenides and other layered crystals in quantum technology to create non-classical light. Currently, the main method of their formation is exfoliation followed by strain and defect engineering. A factor limiting the use of epitaxy is the presence of different phases in the grown films. In this work, we show that control over their formation makes it possible to create structures with the desired properties. We propose Ga2Se3/GaSe nanostructures grown by van der Waals epitaxy with a high VI/III flux ratio as a source of narrow exciton lines. Actually, these nanostructures are a combination of allotropes: GaSe and Ga2Se3, consisting of the same atoms in different arrangements. The energy positions of the narrow lines are determined by the quantum confinement in Ga2Se3 inclusions of different sizes in the GaSe matrix, similar to quantum dots, and their linear polarization is due to the ordering of Ga vacancies in a certain crystalline direction in Ga2Se3. Such nanostructures exhibit single-photon emission with second-order correlation function g(2)(0) ∼ 0.10 at 10 K that makes them promising for quantum technologies.

Ultracompact Single-Photon Sources of Linearly Polarized Vortex Beams.

Ultracompact chip-integrated single-photon sources of collimated beams with polarization-encoded states are crucial for integrated quantum technologies. However, most of currently available single-photon sources rely on external bulky optical components to shape the polarization and phase front of emitted photon beams. Efficient integration of quantum emitters with beam shaping and polarization encoding functionalities remains so far elusive. Here, ultracompact single-photon sources of linearly polarized vortex beams based on chip-integrated quantum emitter-coupled metasurfaces are presented, which are meticulously designed by fully exploiting the potential of nanobrick-arrayed metasurfaces. The authors first demonstrate on-chip single-photon generation of high-purity linearly polarized vortex beams with prescribed topological charges of 0, - 1, and +1. The multiplexing of single-photon emission channels with orthogonal linear polarizations carrying different topological charges are further realized and their entanglement is demonstarated. The work illustrates the potential and feasibility of ultracompact quantum emitter-coupled metasurfaces as a new quantum optics platform for realizing chip-integrated high-dimensional single-photon sources.

Multiple channelling single-photon emission with scattering holography designed metasurfaces.

Channelling single-photon emission in multiple well-defined directions and simultaneously controlling its polarization characteristics is highly desirable for numerous quantum technology applications. We show that this can be achieved by using quantum emitters (QEs) nonradiatively coupled to surface plasmon polaritons (SPPs), which are scattered into outgoing free-propagating waves by appropriately designed metasurfaces. The QE-coupled metasurface design is based on the scattering holography approach with radially diverging SPPs as reference waves. Using holographic metasurfaces fabricated around nanodiamonds with single Ge vacancy centres, we experimentally demonstrate on-chip integrated efficient generation of two well-collimated single-photon beams propagating along different 15° off-normal directions with orthogonal linear polarizations.

Crystal Structure, Raman, FTIR, UV-Vis Absorption, Photoluminescence Spectroscopy, TG-DSC and Dielectric Properties of New Semiorganic Crystals of 2-Methylbenzimidazolium Perchlorate.

Single crystals of 2-methylbenzimidazolium perchlorate were prepared for the first time with a slow evaporation method from an aqueous solution of a mixture of 2-methylbenzimidazole (MBI) crystals and perchloric acid HClO4. The crystal structure was determined by single crystal X-ray diffraction (XRD) and confirmed by XRD of powder. Angle-resolved polarized Raman and Fourier-transform infrared (FTIR) absorption spectra of crystals consist of lines caused by molecular vibrations in MBI molecule and ClO4- tetrahedron in the region ν = 200-3500 cm-1 and lattice vibrations in the region of 0-200 cm-1. Both XRD and Raman spectroscopy show a protonation of MBI molecule in the crystal. An analysis of ultraviolet-visible (UV-Vis) absorption spectra gives an estimation of an optical gap Eg~3.9 eV in the crystals studied. Photoluminescence spectra of MBI-perchlorate crystals consist of a number of overlapping bands with the main maximum at Ephoton ≅ 2.0 eV. Thermogravimetry-differential scanning calorimetry (TG-DSC) revealed the presence of two first-order phase transitions with different temperature hysteresis at temperatures above room temperature. The higher temperature transition corresponds to the melting temperature. Both phase transitions are accompanied by a strong increase in the permittivity and conductivity, especially during melting, which is similar to the effect of an ionic liquid.

Indirect bandgap MoSe2 resonators for light-emitting nanophotonics.

Transition metal dichalcogenides (TMDs) are promising for new generation nanophotonics due to their unique optical properties. However, in contrast to direct bandgap TMD monolayers, bulk samples have an indirect bandgap that restricts their application as light emitters. On the other hand, the high refractive index of these materials allows for effective light trapping and the creation of high-Q resonators. In this work, a method for the nanofabrication of microcavities from indirect TMD multilayer flakes, which makes it possible to achieve pronounced resonant photoluminescence enhancement due to the cavity modes, is proposed. Whispering gallery mode (WGM) resonators are fabricated from bulk indirect MoSe2 using resistless scanning probe lithography. A micro-photoluminescence (µ-PL) investigation revealed the WGM spectra of the resonators with an enhancement factor up to 100. The characteristic features of WGMs are clearly seen from the scattering experiments which are in agreement with the results of numerical simulations. It is shown that the PL spectra in the fabricated microcavities are contributed by two mechanisms demonstrating different temperature dependences. The indirect PL, which is quenched with the temperature decrease, and the direct PL which almost does not depend on the temperature. The results of the work show that the suggested approach has great prospects in nanophotonics.

Multi-Frequency Light Sources Based on CVD Diamond Matrices with a Mix of SiV- and GeV- Color Centers and Tungsten Complexes.

Recently, nanodiamonds with negatively charged luminescent color centers based on atoms of the fourth group (SiV-, GeV-) have been proposed for use as biocompatible luminescent markers. Further improvement of the functionality of such systems by expanding the frequencies of the emission can be achieved by the additional formation of luminescent tungsten complexes in the diamond matrix. This paper reports the creation of diamond matrices by a hot filament chemical vapor deposition method, containing combinations of luminescing Si-V and Ge-V color centers and tungsten complexes. The possibility is demonstrated of creating a multicolor light source combining the luminescence of all embedded emitters. The emission properties of tungsten complexes and Si-V and Ge-V color centers in the diamond matrices were investigated, as well as differences in their luminescent properties and electron-phonon interaction at different temperatures.

Silicon-Vacancy Nanodiamonds as High Performance Near-Infrared Emitters for Live-Cell Dual-Color Imaging and Thermometry.

Nanodiamonds (NDs) with color centers are excellent emitters for various bioimaging and quantum biosensing applications. In our work, we explore new applications of NDs with silicon-vacancy centers (SiV) obtained by high-pressure high-temperature (HPHT) synthesis based on metal-catalyst-free growth. They are coated with a polypeptide biopolymer, which is essential for efficient cellular uptake. The unique optical properties of NDs with SiV are their high photostability and narrow emission in the near-infrared region. Our results demonstrate for the first time that NDs with SiV allow live-cell dual-color imaging and intracellular tracking. Also, intracellular thermometry and challenges associated with SiV atomic defects in NDs are investigated and discussed for the first time. NDs with SiV nanoemitters provide new avenues for live-cell bioimaging, diagnostic (SiV as a nanosized thermometer), and theranostic (nanodiamonds as drug carrier) applications.

The Effect of Interface Diffusion on Raman Spectra of Wurtzite Short-Period GaN/AlN Superlattices.

We present an extensive theoretical and experimental study to identify the effect on the Raman spectrum due to interface interdiffusion between GaN and AlN layers in short-period GaN/AlN superlattices (SLs). The Raman spectra for SLs with sharp interfaces and with different degree of interface diffusion are simulated by ab initio calculations and within the framework of the random-element isodisplacement model. The comparison of the results of theoretical calculations and experimental data obtained on PA MBE and MOVPE grown SLs, showed that the bands related to A1(LO) confined phonons are very sensitive to the degree of interface diffusion. As a result, a correlation between the Raman spectra in the range of A1(LO) confined phonons and the interface quality in SLs is obtained. This opens up new possibilities for the analysis of the structural characteristics of short-period GaN/AlN SLs using Raman spectroscopy.

Creation of Negatively Charged Boron Vacancies in Hexagonal Boron Nitride Crystal by Electron Irradiation and Mechanism of Inhomogeneous Broadening of Boron Vacancy-Related Spin Resonance Lines.

Optically addressable high-spin states (S ≥ 1) of defects in semiconductors are the basis for the development of solid-state quantum technologies. Recently, one such defect has been found in hexagonal boron nitride (hBN) and identified as a negatively charged boron vacancy (VB-). To explore and utilize the properties of this defect, one needs to design a robust way for its creation in an hBN crystal. We investigate the possibility of creating VB- centers in an hBN single crystal by means of irradiation with a high-energy (E = 2 MeV) electron flux. Optical excitation of the irradiated sample induces fluorescence in the near-infrared range together with the electron spin resonance (ESR) spectrum of the triplet centers with a zero-field splitting value of D = 3.6 GHz, manifesting an optically induced population inversion of the ground state spin sublevels. These observations are the signatures of the VB- centers and demonstrate that electron irradiation can be reliably used to create these centers in hBN. Exploration of the VB- spin resonance line shape allowed us to establish the source of the line broadening, which occurs due to the slight deviation in orientation of the two-dimensional B-N atomic plains being exactly parallel relative to each other. The results of the analysis of the broadening mechanism can be used for the crystalline quality control of the 2D materials, using the VB- spin embedded in the hBN as a probe.

Phonons in Short-Period GaN/AlN Superlattices: Group-Theoretical Analysis, Ab initio Calculations, and Raman Spectra.

We report the results of experimental and theoretical studies of phonon modes in GaN/AlN superlattices (SLs) with a period of several atomic layers, grown by submonolayer digital plasma-assisted molecular-beam epitaxy, which have a great potential for use in quantum and stress engineering. Using detailed group-theoretical analysis, the genesis of the SL vibrational modes from the modes of bulk AlN and GaN crystals is established. Ab initio calculations in the framework of the density functional theory, aimed at studying the phonon states, are performed for SLs with both equal and unequal layer thicknesses. The frequencies of the vibrational modes are calculated, and atomic displacement patterns are obtained. Raman spectra are calculated and compared with the experimental ones. The results of the ab initio calculations are in good agreement with the experimental Raman spectra and the results of the group-theoretical analysis. As a result of comprehensive studies, the correlations between the parameters of acoustic and optical phonons and the structure of SLs are obtained. This opens up new possibilities for the analysis of the structural characteristics of short-period GaN/AlN SLs using Raman spectroscopy. The results obtained can be used to optimize the growth technologies aimed to form structurally perfect short-period GaN/AlN SLs.

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.

State-of-the-art and prospects for intense red radiation from core-shell InGaN/GaN nanorods.

Core-shell nanorods (NRs) with InGaN/GaN quantum wells (QWs) are promising for monolithic white light-emitting diodes and multi-color displays. Such applications, however, are still a challenge because intensity of the red band is too weak compared with blue and green. To clarify this problem, we measured photoluminescence of different NRs, depending on power and temperature, as well as with time resolution. These studies have shown that dominant emission bands come from nonpolar and semipolar QWs, while a broad yellow-red band arises mainly from defects in the GaN core. An emission from polar QWs located at the NR tip is indistinguishable against the background of defect-related luminescence. Our calculations of electromagnetic field distribution inside the NRs show a low density of photon states at the tip, which additionally suppresses the radiation of polar QWs. We propose placing polar QWs inside a cylindrical part of the core, where the density of photon states is higher and the well area is much larger. Such a hybrid design, in which the excess of blue radiation from shell QWs is converted to red radiation in core wells, can help solve the urgent problem of red light for many applications of NRs.

Molecular Beam Epitaxy of Layered Group III Metal Chalcogenides on GaAs(001) Substrates.

Development of molecular beam epitaxy (MBE) of two-dimensional (2D) layered materials is an inevitable step in realizing novel devices based on 2D materials and heterostructures. However, due to existence of numerous polytypes and occurrence of additional phases, the synthesis of 2D films remains a difficult task. This paper reports on MBE growth of GaSe, InSe, and GaTe layers and related heterostructures on GaAs(001) substrates by using a Se valve cracking cell and group III metal effusion cells. The sophisticated self-consistent analysis of X-ray diffraction, transmission electron microscopy, and Raman spectroscopy data was used to establish the correlation between growth conditions, formed polytypes and additional phases, surface morphology and crystalline structure of the III-VI 2D layers. The photoluminescence and Raman spectra of the grown films are discussed in detail to confirm or correct the structural findings. The requirement of a high growth temperature for the fabrication of optically active 2D layers was confirmed for all materials. However, this also facilitated the strong diffusion of group III metals in III-VI and III-VI/II-VI heterostructures. In particular, the strong In diffusion into the underlying ZnSe layers was observed in ZnSe/InSe/ZnSe quantum well structures, and the Ga diffusion into the top InSe layer grown at ~450 °C was confirmed by the Raman data in the InSe/GaSe heterostructures. The results on fabrication of the GaSe/GaTe quantum well structures are presented as well, although the choice of optimum growth temperatures to make them optically active is still a challenge.

Formation of interstitial silicon defects in Si- and Si,P-doped nanodiamonds and thermal susceptibilities of SiV- photoluminescence band.

We have produced two types of synthetic nanodiamonds Si- and Si,P-doped and have characterized the thermal susceptibilities of the spectral band of silicon-vacancy (SiV-) centers at approximately 740 nm in each case. The covered temperature range from 295 to 350 K is of interest for thermometry in biological systems. Comparison of the relative brightness of the Si- and Si,P-doped crystals shows that phosphorous significantly increases average concentration and homogeneity of distribution of SiV- centers in nanodiamonds. Moreover, linear dependence on temperature of the zero-phonon line width in Si-doped crystals is 0.061(2) nm K-1 but is 0.047(3) nm K-1, about 35% smaller in Si,P-doped nanodiamonds. This proves control of SiV- properties with additional chemical doping and close proximity of Si and P atoms.

Long-term live cells observation of internalized fluorescent Fe@C nanoparticles in constant magnetic field.

BACKGROUND: Theranostics application of superparamagnetic nanoparticles based on magnetite and maghemite is impeded by their toxicity. The use of additional protective shells significantly reduced the magnetic properties of the nanoparticles. Therefore, iron carbides and pure iron nanoparticles coated with multiple layers of onion-like carbon sheath seem to be optimal for biomedicine. Fluorescent markers associated with magnetic nanoparticles provide reliable means for their multimodal visualization. Here, biocompatibility of iron nanoparticles coated with graphite-like shell and labeled with Alexa 647 fluorescent marker has been investigated. METHODS: Iron core nanoparticles with intact carbon shells were purified by magnetoseparation after hydrochloric acid treatment. The structure of the NPs (nanoparticles) was examined with a high resolution electron microscopy. The surface of the NPs was alkylcarboxylated and further aminated for covalent linking with Alexa Fluor 647 fluorochrome to produce modified fluorescent magnetic nanoparticles (MFMNPs). Live fluorescent imaging and correlative light-electron microscopy were used to study the NPs intracellular distribution and the effects of constant magnetic field on internalized NPs in the cell culture were analyzed. Cell viability was assayed by measuring a proliferative pool with Click-IT labeling. RESULTS: The microstructure and magnetic properties of superparamagnetic Fe@C core-shell NPs as well as their endocytosis by living tumor cells, and behavior inside the cells in constant magnetic field (150 mT) were studied. Correlative light-electron microscopy demonstrated that NPs retained their microstructure after internalization by the living cells. Application of constant magnetic field caused orientation of internalized NPs along power lines thus demonstrating their magnetocontrollability. Carbon onion-like shells make these NPs biocompatible and enable long-term observation with confocal microscope. It was found that iron core of NPs shows no toxic effect on the cell physiology, does not inhibit the cell proliferation and also does not induce apoptosis. CONCLUSIONS: Non-toxic, biologically compatible superparamagnetic fluorescent MFMNPs can be further used for biological application such as delivery of biologically active compounds both inside the cell and inside the whole organism, magnetic separation, and magnetic resonance imaging (MRI) diagnostics.

Mechanism of Transformation of Ferrocene into Carbon-Encapsulated Iron Carbide Nanoparticles at High Pressures and Temperatures.

A mechanism was established for the formation of nanosized iron carbide particles encapsulated in carbon shells via the processes of ferrocene thermal conversions at high pressures. At a pressure of 8.0 GPa, products of ferrocene decomposition were studied as a function of temperature by X-ray diffraction, Raman and Mössbauer spectroscopy, scanning and transmission electron microscopy. It was shown that the mechanism of formation of the carbon-encapsulated iron carbide nanoparticles at high pressures and temperatures differs qualitatively from the known mechanism of their formation in the gas-phase processes of laser pyrolysis or photolysis of ferrocene. At high pressures and temperatures, the formation of iron carbide nanoparticles occurs not due to the primary growth of pure iron particles and the subsequent dissolution of carbon in iron. Nanoparticles are formed due to the direct fusion of iron-carbon clusters, which are formed at intermediate stages of ferrocene thermal destruction. Then, obtained amorphous iron carbides Fe1- xC x with a high carbon content start to crystallize. Two crystalline carbon-encapsulated forms of iron carbide (Fe7C3 and Fe3C) are the main products of crystallization of the amorphous Fe1- xC x depending on the temperature of the ferrocene treatment.

On-chip excitation of single germanium vacancies in nanodiamonds embedded in plasmonic waveguides.

Monolithic integration of quantum emitters in nanoscale plasmonic circuitry requires low-loss plasmonic configurations capable of confining light well below the diffraction limit. We demonstrated on-chip remote excitation of nanodiamond-embedded single quantum emitters by plasmonic modes of dielectric ridges atop colloidal silver crystals. The nanodiamonds were produced to incorporate single germanium-vacancy (GeV) centres, providing bright, spectrally narrow and stable single-photon sources suitable for highly integrated circuits. Using electron-beam lithography with hydrogen silsesquioxane (HSQ) resist, dielectric-loaded surface plasmon polariton waveguides (DLSPPWs) were fabricated on single crystalline silver plates to contain those of deposited nanodiamonds that are found to feature appropriate single GeV centres. The low-loss plasmonic configuration enabled the 532-nm pump laser light to propagate on-chip in the DLSPPW and reach to an embedded nanodiamond where a single GeV centre was incorporated. The remote GeV emitter was thereby excited and coupled to spatially confined DLSPPW modes with an outstanding figure-of-merit of 180 due to a ~six-fold Purcell enhancement, ~56% coupling efficiency and ~33 µm transmission length, thereby opening new avenues for the implementation of nanoscale functional quantum devices.

Unified mechanism of the surface Fermi level pinning in III-As nanowires.

Fermi level pinning at the oxidized (110) surfaces of III-As nanowires (GaAs, InAs, InGaAs, AlGaAs) is studied. Using scanning gradient Kelvin probe microscopy, we show that the Fermi level at oxidized cleavage surfaces of ternary Al x Ga1-x As (0 ≤ x ≤ 0.45) and Ga x In1-x As (0 ≤ x ≤ 1) alloys is pinned at the same position of 4.8 ± 0.1 eV with regard to the vacuum level. The finding implies a unified mechanism of the Fermi level pinning for such surfaces. Further investigation, performed by Raman scattering and photoluminescence spectroscopy, shows that photooxidation of the Al x Ga1-x As and Ga x In1-x As nanowires leads to the accumulation of an excess of arsenic on their crystal surfaces which is accompanied by a strong decrease of the band-edge photoluminescence intensity. We conclude that the surface excess arsenic in crystalline or amorphous forms is responsible for the Fermi level pinning at oxidized (110) surfaces of III-As nanowires.

Varying temperature and silicon content in nanodiamond growth: effects on silicon-vacancy centres.

Nanodidamonds containing colour centres open up many applications in quantum information processing, metrology, and quantum sensing. However, controlling the synthesis of nanodiamonds containing silicon vacancy (SiV) centres is still not well understood. Here we study nanodiamonds produced by a high-pressure high-temperature method without catalyst metals, focusing on two samples with clear SiV signatures. Different growth temperatures and relative content of silicon in the initial compound between the samples altered their nanodiamond size distributions and abundance of SiV centres. Our results show that nanodiamond growth can be controlled and optimised for different applications.