Optical Properties of Bulk Single-Crystal Diamonds at 80–1200 K by Vibrational Spectroscopic Methods

Bulk diamonds show great potential for optical applications such as for use in infrared (IR) windows and temperature sensors. The development of optical-grade bulk diamond synthesis techniques has facilitated its extreme applications. Here, two kinds of bulk single-crystal diamonds, a high-pressure and high-temperature (HPHT) diamond and a chemical vapor deposition (CVD) diamond, were evaluated by Raman spectroscopy and Fourier Transform Infra-Red (FTIR) spectroscopy at a range of temperatures from 80 to 1200 K. The results showed that there was no obvious difference between the HPHT diamond and the CVD diamond in terms of XRD and Raman spectroscopy at 300–1200 K. The measured nitrogen content was ~270 and ~0.89 ppm for the HPHT diamond and the CVD diamond, respectively. The moderate nitrogen impurities did not significantly affect the temperature dependence of Raman spectra for temperature-sensing applications. However, the nitrogen impurities greatly influence FTIR spectroscopy and optical transmittance. The CVD diamond showed higher transmittance, up to 71% with only a ~6% drop at temperatures as high as 873 K. This study shows that CVD bulk diamonds can be used for IR windows under harsh environments.     

Boron-Doped Diamond/GaN Heterojunction—The Influence of the Low-Temperature Deposition

We report a method of growing a boron-doped diamond film by plasma-assisted chemical vapour deposition utilizing a pre-treatment of GaN substrate to give a high density of nucleation. CVD diamond was deposited on GaN substrate grown epitaxially via the molecular-beam epitaxy process. To obtain a continuous diamond film with the presence of well-developed grains, the GaN substrates are exposed to hydrogen plasma prior to deposition. The diamond/GaN heterojunction was deposited in methane ratio, chamber pressure, temperature, and microwave power at 1%, 50 Torr, 500 °C, and 1100 W, respectively. Two samples with different doping were prepared 2000 ppm and 7000 [B/C] in the gas phase. SEM and AFM analyses revealed the presence of well-developed grains with an average size of 100 nm. The epitaxial GaN substrate-induced preferential formation of (111)-facetted diamond was revealed by AFM and XRD. After the deposition process, the signal of the GaN substrate is still visible in Raman spectroscopy (showing three main GaN bands located at 565, 640 and 735 cm⁻¹) as well as in typical XRD patterns. Analysis of the current–voltage characteristics as a function of temperature yielded activation energy equal to 93.8 meV.     

Synthesis of Copper Nitride Layers by the Pulsed Magnetron Sputtering Method Carried out under Various Operating Conditions

Copper nitride shows various properties that depend on the structure of the material and is influenced by the change in technical parameters. In the present work, Cu–N layers were synthesized using the pulsed magnetron sputtering method. The synthesis was performed under different operating conditions: direct current (DC) or alternating current (AC) power supply, and various atmospheres: pure Ar and a mixture of Ar + N₂. The structural properties of the deposited layers were characterized by X-ray diffraction measurements, and Raman spectroscopy and scanning electron microscopy have been performed. Optical properties were also evaluated. The obtained layers showed tightly packed columnar grain features. The kinetics of the layer growth in the AC mode was lower than that observed in the DC mode, and the layers were thinner and more fine-grained. The copper nitride layers were characterized by the one-phase and two-phase polycrystalline structure of the Cu₃N phase with the preferred growth orientation (100). The lattice constant oscillates between 3.808 and 3.815 Å for one-phase and has a value of 3.828 Å for a two-phase structure. Phase composition results were correlated with Raman spectroscopy measurements. Raman spectra exhibited a broad, diffused, and intense signal of Cu₃N phase, with Raman shift located at 628–635 cm⁻¹. Studies on optical properties showed that the energy gap ranged from 2.17 to 2.47 eV. The results showed that controlling technical parameters gives a possibility to optimize the structure and phase composition of deposited layers. The reported changes were discussed and attributed to the properties of the material layers and technology method.     

Vanadia–Zirconia and Vanadia–Hafnia Catalysts for Utilization of Volatile Organic Compound Emissions

Utilization is a sustainable and interesting alternative for the destructive treatment of volatile organic compounds due to avoided CO₂ emission. This work concentrates on the development of active and sulfur-tolerant catalysts for the utilization of contaminated methanol. Impregnated and sol–gel prepared vanadia–zirconia and vanadia–hafnia catalysts were thoroughly characterized by N₂ sorption, analytical (S)TEM, elemental analysis, XRD and Raman spectroscopy, and their performances were evaluated in formaldehyde production from methanol and methanethiol mixture. The results showed higher activity of the sol–gel prepared catalysts due to formation of mono- and polymeric vanadia species. Unfortunately, the most active vanadia sites were deactivated more easily than the metal-mixed oxide HfV₂O₇ and ZrV₂O₇ phases, as well as crystalline V₂O₅ observed in the impregnated catalysts. Metal-mixed oxide phases were formed in impregnated catalysts through formation of defects in HfO₂ and ZrO₂ structure during calcination at 600 °C, which was evidenced by Raman spectroscopy. The sol–gel prepared vanadia–zirconia and vanadia–hafnia catalysts were able to produce formaldehyde from contaminated methanol with high selectivity at temperature around 400 °C, while impregnated catalysts required 50–100 °C higher temperatures.     

Epitaxial Growth and Characterization of 4H-SiC for Neutron Detection Applications

The purpose of this work is to study the 4H-SiC epitaxial layer properties for the fabrication of a device for neutron detection as an alternative material to diamond detectors used in this field. We have studied a high growth rate process to grow a thick epitaxial layer (250 µm) of 4H-SiC and, in order to estimate the quality of the epitaxial layer, an optical characterization was done through Photoluminescence (PL) spectroscopy for stacking fault defect evaluation. Micro Raman spectroscopy was used for simultaneous determination of both carrier lifetime and induced carriers in equilibrium. We have compared these results with other two samples with an epitaxial layer of 100 micron, obtained with two different growth rates, 60 and 90 µm/h, respectively. From Raman measurements it has been observed that both the growth rate and the grown epitaxial layer thickness have an effect on the measured carrier lifetime. A comparison between different kinds of stacking faults (SF) was done, evaluating the influence of these defects on the carrier lifetime as a function of the injection level and it was observed that only at a low injection is the effect on the carrier lifetime low.     

Rapid Growth of Nanostructured Diamond Film on Silicon and Ti–6Al–4V Alloy Substrates

Nanostructured diamond (NSD) films were grown on silicon and Ti–6Al–4V alloy substrates by microwave plasma chemical vapor deposition (MPCVD). NSD Growth rates of 5 μm/h on silicon, and 4 μm/h on Ti–6Al–4V were achieved. In a chemistry of H₂/CH₄/N₂, varying ratios of CH₄/H₂ and N₂/CH₄ were employed in this research and their effect on the resulting diamond films were studied by X-ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, and atomic force microscopy. As a result of modifying the stock cooling stage of CVD system, we were able to utilize plasma with high power densities in our NSD growth experiments, enabling us to achieve high growth rates. Substrate temperature and N₂/CH₄ ratio have been found to be key factors in determining the diamond film quality. NSD films grown as part of this study were shown to contain 85% to 90% sp³ bonded carbon.     

Study of Radiation-Induced Defects in p-Type Si1−xGex Diodes before and after Annealing

In this work, electrically active defects of pristine and 5.5 MeV electron irradiated p-type silicon–germanium (Si_1−xGe_x)-based diodes were examined by combining regular capacitance deep-level transient spectroscopy (C-DLTS) and Laplace DLTS (L-DLTS) techniques. The p-type SiGe alloys with slightly different Ge contents were examined. It was deduced from C-DLTS and L-DLTS spectra that the carbon/oxygen-associated complexes prevailed in the pristine Si_0.949Ge_0.051 alloys. Irradiation with 5.5 MeV electrons led to a considerable change in the DLT spectrum containing up to seven spectral peaks due to the introduction of radiation defects. These defects were identified using activation energy values reported in the literature. The double interstitial and oxygen complexes and the vacancy, di-vacancy and tri-vacancy ascribed traps were revealed in the irradiated samples. The interstitial carbon and the metastable as well as stable forms of carbon–oxygen (C_iO_i^* and C_iO_i) complexes were also identified for the electron-irradiated SiGe alloys. It was found that the unstable form of the carbon–oxygen complex became a stable complex in the irradiated and the subsequently annealed (at 125 °C) SiGe samples. The activation energy shifts in the radiation-induced deep traps to lower values were defined when increasing Ge content in the SiGe alloy.     

Observation of water dangling OH bonds around dissolved nonpolar groups

We report the experimental observation of water dangling OH bonds in the hydration shells around dissolved nonpolar (hydrocarbon) groups. The results are obtained by combining vibrational (Raman) spectroscopy and multivariate curve resolution (MCR), to reveal a high-frequency OH stretch peak arising from the hydration shell around nonpolar (hydrocarbon) solute groups. The frequency and width of the observed peak is similar to that of dangling OH bonds previously detected at macroscopic air–water and oil–water interfaces. The area of the observed peak is used to quantify the number of water dangling bonds around hydrocarbon chains of different length. Molecular dynamics simulation of the vibrational spectra of water molecules in the hydration shell around neopentane and benzene reveals high-frequency OH features that closely resemble the experimentally observed dangling OH vibrational bands around neopentyl alcohol and benzyl alcohol. The red-shift of ≈50 cm⁻¹ induced by aromatic solutes is similar to that previously observed upon formation of a π-H bond (in low-temperature benzene–water clusters).     

Fluorine-Terminated Polycrystalline Diamond Solution-Gate Field-Effect Transistor Sensor with Smaller Amount of Unexpectedly Generated Fluorocarbon Film Fabricated by Fluorine Gas Treatment

In this study, a partially fluorine-terminated solution-gate field-effect transistor sensor with a smaller amount of unexpectedly generated fluorohydrocarbon film on a polycrystalline diamond channel is described. A conventional method utilizing inductively coupled plasma with fluorocarbon gas leads the hydrogen-terminated diamond to transfer to a partially fluorine-terminated diamond (C–F diamond); an unexpected fluorohydrocarbon film is formed on the surface of the diamond. To overcome this issue, we newly applied fluorine gas for the fluoridation of the diamond. Analytical results of X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry suggest that the fluorocarbon film does not exist or only a smaller amount of fluorocarbon film exists on the diamond surface. Conversely, the C–F diamond fabricated by the conventional method of inductively coupled plasma with a perfluoropropane gas (C₃F₈ gas) source possesses a certain amount of fluorocarbon film on its surface. The C–F diamond with a smaller amount of unexpectedly generated fluorohydrocarbon film possesses nearly ideal drain–source–voltage vs. gate–source–current characteristics, corresponding to metal–oxide–silicon semiconductor field-effect transistor theory. The results indicate that the fluorine gas (F₂ gas) treatment proposed in this study effectively fabricates a C–F diamond sensor without unexpected semiconductor damage.     

Correlation between Defects and Electrical Performances of Ion-Irradiated 4H-SiC p–n Junctions

In this study, 4H-SiC p–n junctions were irradiated with 700 keV He⁺ ions in the fluence range 1.0 × 10¹² to 1.0 × 10¹⁵ ions/cm². The effects of irradiation were investigated by current–voltage (I–V) and capacitance–voltage (C–V) measurements, while deep-level transient spectroscopy (DLTS) was used to study the traps introduced by irradiation defects. Modifications of the device’s electrical performances were observed after irradiation, and two fluence regimes were identified. In the low fluence range (≤10¹³ ions/cm²), I–V characteristics evidenced an increase in series resistance, which can be associated with the decrease in the dopant concentration, as also denoted by C–V measurements. In addition, the pre-exponential parameter of junction generation current increased with fluence due to the increase in point defect concentration. The main produced defect states were the Z_1/2, RD_1/2, and EH_6/7 centers, whose concentrations increased with fluence. At high fluence (>10¹³ ions/cm²), I–V curves showed a strong decrease in the generation current, while DLTS evidenced a rearrangement of defects. The detailed electrical characterization of the p–n junction performed at different temperatures highlights the existence of conduction paths with peculiar electrical properties introduced by high fluence irradiation. The results suggest the formation of localized highly resistive regions (realized by agglomeration of point defects) in parallel with the main junction.     

Reducing Threading Dislocations of Single-Crystal Diamond via In Situ Tungsten Incorporation

A lower dislocation density substrate is essential for realizing high performance in single-crystal diamond electronic devices. The in-situ tungsten-incorporated homoepitaxial diamond by introducing tungsten hexacarbonyl has been proposed. A 3 × 3 × 0.5 mm³ high-pressure, high-temperature (001) diamond substrate was cut into four pieces with controlled experiments. The deposition of tungsten-incorporated diamond changed the atomic arrangement of the original diamond defects so that the propagation of internal dislocations could be inhibited. The SEM images showed that the etching pits density was significantly decreased from 2.8 × 10⁵ cm⁻² to 2.5 × 10³ cm⁻². The reduction of XRD and Raman spectroscopy FWHM proved that the double-layer tungsten-incorporated diamond has a significant effect on improving the crystal quality of diamond bulk. These results show the evident impact of in situ tungsten-incorporated growth on improving crystal quality and inhibiting the dislocations propagation of homoepitaxial diamond, which is of importance for high-quality diamond growth.     

Development of Conductive Boron-Doped Diamond Electrode: A microscopic,Spectroscopic, and Voltammetric Study

Building on diamond characteristics such as hardness, chemical inertness and low electron emission threshold voltage, the current microscopic, spectroscopic and voltammetric investigations are directed towards improving the properties of electrode coating materials for their future use in clinical studies of deep brain stimulation via fast-scan cyclic voltammetry (FSCV). In this study we combine the capabilities of confocal Raman mapping in providing detailed and accurate analysis of local distributions of material constituents in a series of boron-doped polycrystalline diamond films grown by chemical vapor deposition, with information from the more conventional techniques of scanning electron microscopy (SEM) and infrared absorption spectroscopy. Although SEM images show a uniform distribution of film crystallites, they have the limitation of being unable to differentiate the distribution of boron in the diamond. Values of 10¹⁸–10²¹ atoms/cm³ of boron content have been estimated from the absorption coefficient of the 1290 cm⁻¹ infrared absorption band and from the 500 cm⁻¹ Raman vibration. The observed accumulation of boron atoms and carbon sp² impurities at the grain boundaries suggests that very high doping levels do not necessarily contribute to improvement of the material’s conductivity, corroborating with voltammetric data. FSCV results also indicate an enhanced stability of analyte detection.     

Effect of Different Rotational Speeds on Graphene-Wrapped SiC Core-Shell Nanoparticles in Wet Milling Medium

The effects of the wet milling rotating speed on the number of graphene layers and graphene quality, and the conversion efficiency of graphite exfoliate to graphene, were investigated by scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). The results show that the number of few-layer graphene nanometer sheets (GNSs) (≤10 layers) gradually increases with the increase of rotational speed in the range of 160–240 rpm. The proportion of GNSs with 0–10 layers reaches more than 80% as the rotational speed is increased to 280 rpm. GNS defect types in the composite materials are marginal defects with minimal influence and almost no oxidation. In the range of 160–280 rpm, the intensity of graphite peak decreases and the conversion efficiency of graphene increases with the increase of rotational speed. This is the same as the experimental result obtained by HRTEM.     

The Performance of Graphene-Enhanced THz Grating: Impact of the Gold Layer Imperfectness

We report the performance of a graphene-enhanced THz grating fabricated by depositing a gold layer on the femtosecond micromachined SiO₂ substrate. The morphology of the gold plated patterned substrate was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM), while the quality of the chemical vapor deposition (CVD) graphene was evaluated by Raman spectroscopy. The electromagnetic (EM) response of the metasurface comprising the graphene sheet and the gold plated substrate was studied by THz time domain spectroscopy in the 100 GHz–1 THz frequency range. We employed the finite elements method (FEM) to model the metasurface EM response by adjusting the ac conductivity of the gold layer covering the patterned SiO₂ substrate to reproduce the measured transmission/reflection spectra. The results of the numerical simulation reveal the impact of the imperfectness of the gold layer on the performance of the THz metasurface. The experimental results are well described in terms of the Drude–Smith model of metal conductivity that takes into account the anisotropic scattering of the carriers in thin metal films.     

The Synthesis of α-MoO3 by Ethylene Glycol

This study investigated the use of ethylene glycol to form α-MoO₃ (molybdenum trioxide) from ammonium molybdate tetrahydrate at various sintering temperatures for 1 h. During the sintering process, the morphologies of the constituents were observed using scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) spectroscopy was used to explain the reaction process. In this work, the results obtained using X-ray photoelectron spectroscopy (XRD) demonstrated that, when the molybdenum trioxide powder was treated thermally at 300 °C, the material exhibited crystallinity. The peaks were indexed to correspond with the (110), (040), (021), (111), and (060) crystallographic planes, and the lattice parameters of a, b, and c were about 3.961, 13.876, and 3.969 Å. Using these observations, we confirmed that orthorhombic α-MoO₃ was formed for sintering temperatures from 300 to 700 °C. Pattern images were obtained by the selected area electron diffraction pattern (SAED) technique, and the d distance of the high resolution transmission electron microscopy (HRTEM) images were almost 0.39 and 0.36 nm, and the Mo 3d_5/2, Mo 3d_3/2, and O 1s of X-ray photoelectron spectroscopy (XPS) were located at 233.76, 237.03, and 532.19 eV, which also demonstrated that α-MoO₃ powder had been synthesized.     

Conformational isomerization kinetics of pent-1-en-4-yne with 3,330 cm-1 of internal energy measured by dynamic rotational spectroscopy

We demonstrate the application of molecular rotational spectroscopy to measure the conformation isomerization rate of vibrationally excited pent-1-en-4-yne (pentenyne). The rotational spectra of single quantum states of pentenyne are acquired by using a combination of IR–Fourier transform microwave double-resonance spectroscopy and high-resolution, single-photon IR spectroscopy. The quantum states probed in these experiments have energy eigenvalues of ≈3,330 cm⁻¹ and lie above the barrier to conformational isomerization. At this energy, the presence of intramolecular vibrational energy redistribution (IVR) is indicated through the extensive local perturbations found in the high-resolution rotation–vibration spectrum of the acetylenic C–H stretch normal-mode fundamental. The fact that the IVR process produces isomerization is deduced through a qualitatively different appearance of the excited-state rotational spectra compared with the pure rotational spectra of pentenyne. The rotational spectra of the vibrationally excited molecular eigenstates display coalescence between the characteristic rotational frequencies of the stable cis and skew conformations of the molecule. This coalescence is observed for quantum states prepared from laser excitation originating in the ground vibrational state of either of the two stable conformers. Experimental isomerization rates are extracted by using a three-state Bloch model of the dynamic rotational spectra that includes the effects of chemical exchange between the stable conformations. The time scale for the conformational isomerization rate of pentenyne at total energy of 3,330 cm⁻¹ is ≈25 ps and is 50 times slower than the microcanonical isomerization rate predicted by the statistical Rice–Ramsperger–Kassel–Marcus theory.     

First-Principles Simulation of Dielectric Function in Biomolecules

The dielectric spectra of complex biomolecules reflect the molecular heterogeneity of the proteins and are particularly important for the calculations of electrostatic (Coulomb) and electrodynamic (van der Waals) interactions in protein physics. The dielectric response of the proteins can be decomposed into different components depending on the size, structure, composition, locality, and environment of the protein in general. We present a new robust simulation method anchored in rigorous ab initio quantum mechanical calculations of explicit atomistic models, without any indeterminate parameters to compute and gain insight into the dielectric spectra of small proteins under different conditions. We implement this methodology to a polypeptide RGD-4C (1FUV) in different environments, and the SD1 domain in the spike protein of SARS-COV-2. Two peaks at 5.2–5.7 eV and 14.4–15.2 eV in the dielectric absorption spectra are observed for 1FUV and SD1 in vacuum as well as in their solvated and salted models.     

Positron Annihilation Spectroscopy Complex for Structural Defect Analysis in Metal–Hydrogen Systems

The current work is devoted to developing a system for the complex research of metal–hydrogen systems, including in an in situ mode. The system consists of a controlled gas reactor with a unique reaction chamber, a radioisotope positron source, and a positron annihilation spectroscopy complex. The use of the system enables in situ investigation of the defect structure of solids in hydrogen sorption–desorption processes at temperatures up to 900 °C and pressures up to 50 bar. Experimental investigations of magnesium and magnesium hydride during thermal annealing were carried out to approve the possibilities of the developed complex. It was shown that one cycle of magnesium hydrogenation–dehydrogenation resulted in the accumulation of irreversible hydrogen-induced defects. The defect structure investigation of the magnesium–hydrogen system by positron annihilation techniques was supplemented with a comprehensive study by scanning electron microscopy, X-ray diffraction analysis, and hydrogen sorption–desorption studies.     

Ultrasound-Assisted Surface Modification of MWCNT Using Organic Acids

In the present work, multiple-wall carbon nanotubes (MWCNTs) were surface modified in an environmentally friendly way, using low-frequency ultrasonic energy. This type of modification was carried-out using two different types of organic acids, citric acid (CA) and oxalic acid (OA). The modification of the MWCNTs was confirmed by Fourier-transform infrared spectroscopy (FTIR), where functional groups such as OH, C=O, O–C=O and COOH were detected. By means of Raman spectroscopy, an increase in carbon surface defects was found. On the other hand, using X-ray photoelectron spectroscopy (XPS), oxidation was evidenced on the surface of the modified MWCNT. In both Raman spectroscopy and XPS, the results indicate a greater modification when CA is used, possibly due to the fact that CA has a larger number of functional groups. MWCNT-CA showed good dispersion in methanol, while MWCNT-OA showed good stability in methanol and ethanol. Finally, a 20% removal of creatinine efficiency improvement was found with respect to the unmodified MWCNTs, while no improvement was found in the case of urea and uric acid.     

Influence of Diamond Grain Size on the Basic Properties of WC-Co/Diamond Composites Used in Tools for Wood-Based Materials Machining

The paper presents the effect of diamond particle size (varying between 2.5 µm and 20 µm) on the microstructure, density and hardness of WC-Co/diamond composites. The obtained materials contained 30% vol. diamond. The advanced sintering method Pulse Plasma Sintering (PPS) was used for the production of composites. The sintering process was carried out in two stages at a pressure of 50 and 100 MPa and a temperature of 1050 °C. Depending on the size of the diamond particles, composites with a density of 91–99% were obtained. Microstructure studies were performed employing scanning electron microscopy, along with an analysis of the chemical composition in micro-areas. Additionally, the phase composition was investigated by means of X-ray diffraction. In addition, hardness tests were performed. It was found that the size of the diamond particles significantly influenced the microstructure of the tested materials, as well as the density and hardness. As a result of PPS sintering of composites containing the finest diamond particles (2.5–5 µm), the presence of a metastable type of diamond—graphite was found.