Real-Time Ratiometric Optical Nanoscale Thermometry.

All-optical nanothermometry has become a powerful, remote tool for measuring nanoscale temperatures in applications ranging from medicine to nano-optics and solid-state nanodevices. The key features of any candidate nanothermometer are brightness, sensitivity, and (signal, spatial, and temporal) resolution. Here, we demonstrate a real-time, diamond-based nanothermometry technique with excellent sensitivity (1.8% K-1) and record-high resolution (5.8 × 104 K Hz-1/2 W cm-2) based on codoped nanodiamonds. The distinct performance of our approach stems from two factors: (i) temperature sensors─nanodiamonds cohosting two group IV color centers─engineered to emit spectrally separated Stokes and anti-Stokes fluorescence signals under excitation by a single laser source and (ii) a parallel detection scheme based on filtering optics and high-sensitivity photon counters for fast readout. We demonstrate the performance of our method by monitoring temporal changes in the local temperature of a microcircuit and a MoTe2 field-effect transistor. Our work advances a powerful, alternative strategy for time-resolved temperature monitoring and mapping of micro-/nanoscale devices such as microfluidic channels, nanophotonic circuits, and nanoelectronic devices, as well as complex biological environments such as tissues and cells.

Size-Dependent Thermal Stability and Optical Properties of Ultra-Small Nanodiamonds Synthesized under High Pressure.

Diamond properties down to the quantum-size region are still poorly understood. High-pressure high-temperature (HPHT) synthesis from chloroadamantane molecules allows precise control of nanodiamond size. Thermal stability and optical properties of nanodiamonds with sizes spanning range from <1 to 8 nm are investigated. It is shown that the existing hypothesis about enhanced thermal stability of nanodiamonds smaller than 2 nm is incorrect. The most striking feature in IR absorption of these samples is the appearance of an enhanced transmission band near the diamond Raman mode (1332 cm-1). Following the previously proposed explanation, we attribute this phenomenon to the Fano effect caused by resonance of the diamond Raman mode with continuum of conductive surface states. We assume that these surface states may be formed by reconstruction of broken bonds on the nanodiamond surfaces. This effect is also responsible for the observed asymmetry of Raman scattering peak. The mechanism of nanodiamond formation in HPHT synthesis is proposed, explaining peculiarities of their structure and properties.

Structural and Optical Properties of Silicon Carbide Powders Synthesized from Organosilane Using High-Temperature High-Pressure Method.

The development of new strategies for the mass synthesis of SiC nanocrystals with high structure perfection and narrow particle size distribution remains in demand for high-tech applications. In this work, the size-controllable synthesis of the SiC 3C polytype, free of sp2 carbon, with high structure quality nanocrystals, was realized for the first time by the pyrolysis of organosilane C12H36Si6 at 8 GPa and temperatures up to 2000 °C. It is shown that the average particle size can be monotonically changed from ~2 nm to ~500 nm by increasing the synthesis temperature from 800 °C to 1400 °C. At higher temperatures, further enlargement of the crystals is impeded, which is consistent with the recrystallization mechanism driven by a decrease in the surface energy of the particles. The optical properties investigated by IR transmission spectroscopy, Raman scattering, and low-temperature photoluminescence provided information about the concentration and distribution of carriers in nanoparticles, as well as the dominant type of internal point defects. It is shown that changing the growth modes in combination with heat treatment enables control over not only the average crystal size, but also the LO phonon-plasmon coupled modes in the crystals, which is of interest for applications related to IR photonics.

Spontaneous Light Emission Assisted by Mie Resonances in Diamond Nanoparticles.

Spontaneous light emission is known to be affected by the local density of states and enhanced when coupled to a resonant cavity. Here, we report on an experimental study of silicon-vacancy (SiV) color center fluorescence and spontaneous Raman scattering from subwavelength diamond particles supporting low-order Mie resonances in the visible range. For the first time to our knowledge, we have measured the size dependences of the SiV fluorescence emission rate and the Raman scattering intensity from individual diamond particles in the range from 200 to 450 nm. The obtained dependences reveal a sequence of peaks, which we explicitly associate with specific multipole resonances. The results are in agreement with our theoretical analysis and highlight the potential of intrinsic optical resonances for developing nanodiamond-based lasers and single-photon sources.

Boron-Doped Nanodiamonds as Anticancer Agents: En Route to Hyperthermia/Thermoablation Therapy.

Local targeted "inside-out" hyperthermia of tumors via nanoparticles is able to sensitize tumor cells to chemotherapy, radiation therapy, gene therapy, immunotherapy, or other effects, significantly reducing the duration and intensity of treatment. In this article, new nanomaterials are proposed to be used as anticancer agents: boron-doped nanodiamonds with sizes of about 10 nm synthesized for the first time by the high-temperature high-pressure (HTHP) method. The heating ability of boron-doped nanodiamonds was investigated under different heating conditions in different environments: water, chicken egg white, and MCF-7 breast cancer cells. It was discovered that, with the same conversion of the absorbed energy into heat, the ability to heat the environment when excited at a wavelength of 808 nm of boron-doped nanodiamonds is much higher than that of detonation nanodiamonds. It was established that boron-doped nanodiamonds are extremely promising for carrying out hyperthermia and thermoablation of tumors.

Anti-Stokes excitation of solid-state quantum emitters for nanoscale thermometry.

Color centers in solids are the fundamental constituents of a plethora of applications such as lasers, light-emitting diodes, and sensors, as well as the foundation of advanced quantum information and communication technologies. Their photoluminescence properties are usually studied under Stokes excitation, in which the emitted photons are at a lower energy than the excitation ones. In this work, we explore the opposite anti-Stokes process, where excitation is performed with lower-energy photons. We report that the process is sufficiently efficient to excite even a single quantum system-namely, the germanium-vacancy center in diamond. Consequently, we leverage the temperature-dependent, phonon-assisted mechanism to realize an all-optical nanoscale thermometry scheme that outperforms any homologous optical method used to date. Our results frame a promising approach for exploring fundamental light-matter interactions in isolated quantum systems and harness it toward the realization of practical nanoscale thermometry and sensing.

High-Pressure Synthesis of Boron-Doped Ultrasmall Diamonds from an Organic Compound.

The first application of the high-pressure-high-temperature (HPHT) technique for direct production of doped ultrasmall diamonds starting from a one-component organic precursor is reported. Heavily boron-doped diamond nanoparticles with a size below 10 nm are produced by HPHT treatment of 9-borabicyclo [3,3,1]nonane dimer molecules.

Global and local superconductivity in boron-doped granular diamond.

Strong granularity-correlated and intragrain modulations of the superconducting order parameter are demonstrated in heavily boron-doped diamond situated not yet in the vicinity of the metal-insulator transition. These modulations at the superconducting state (SC) and at the global normal state (NS) above the resistive superconducting transition, reveal that local Cooper pairing sets in prior to the global phase coherence.

High-pressure high-temperature synthesis and structure of α-tetragonal boron.

Microcrystals of α-tetragonal (α-t) boron with unit cell parameters a=9.05077(6) and c=5.13409(6) Å and measured density 2.16-2.22 g cm-3 were obtained by pyrolysis of decaborane B10H14 at pressures of 8-9 GPa and temperatures of 1100-1600 ○C. The crystal structure is in good agreement with the model proposed by Hoard et al (1958 J. Am. Chem. Soc.80 4507). However, compared to the original model, we found small deformations of icosahedra and changes in the interatomic distances within the unit cell of the synthesized α-t boron.

Structure and superconductivity of isotope-enriched boron-doped diamond.

Superconducting boron-doped diamond samples were synthesized with isotopes of 10B, 11B, 13C and 12C. We claim the presence of a carbon isotope effect on the superconducting transition temperature, which supports the 'diamond-carbon'-related nature of superconductivity and the importance of the electron-phonon interaction as the mechanism of superconductivity in diamond. Isotope substitution permits us to relate almost all bands in the Raman spectra of heavily boron-doped diamond to the vibrations of carbon atoms. The 500 cm-1 Raman band shifts with either carbon or boron isotope substitution and may be associated with vibrations of paired or clustered boron. The absence of a superconducting transition (down to 1.6 K) in diamonds synthesized in the Co-C-B system at 1900 K correlates with the small boron concentration deduced from lattice parameters.