Ultrafast Infrared Laser Crystallization of Amorphous Ge Films on Glass Substrates.

Amorphous germanium films on nonrefractory glass substrates were annealed by ultrashort near-infrared (1030 nm, 1.4 ps) and mid-infrared (1500 nm, 70 fs) laser pulses. Crystallization of germanium irradiated at a laser energy density (fluence) range from 25 to 400 mJ/cm2 under single-shot and multishot conditions was investigated using Raman spectroscopy. The dependence of the fraction of the crystalline phase on the fluence was obtained for picosecond and femtosecond laser annealing. The regimes of almost complete crystallization of germanium films over the entire thickness were obtained (from the analysis of Raman spectra with excitation of 785 nm laser). The possibility of scanning laser processing is shown, which can be used to create films of micro- and nanocrystalline germanium on flexible substrates.

Thin V2O5 films synthesized by plasma-enhanced atomic layer deposition for memristive applications.

In the present study, the V2O5 films synthesized by plasma-enhanced atomic layer deposition on p-Si and fluorinated graphene on Si (or FG/Si) substrates were analyzed for memristive applications. A number of samples were grown with V2O5 films with an average thickness of 1.0-10.0 nm, as determined by ellipsometric measurements. The study of surface morphology by atomic force microscopy showed that an island growth occurs in the initial stages of the film growth. The Raman spectra of the synthesized V2O5 films with an average thickness of more than 2.0 nm on the SiO2/Si substrates exhibit six distinct modes typical of the orthorhombic V2O5 phase. A large hysteresis was found in the C-V characteristics of the V2O5 films with a thickness of 1.0-4.2 nm. In general, the built-in charge in the V2O5 layers with an average thickness of 1.0-4.0 nm is positive and has a value of about ∼(2-8) × 1011 cm-2 at the 1 MHz frequency. Increasing the V2O5 film thickness leads to the accumulation of negative built-in charge up to -(1.7 to 2.3) × 1011 cm-2 at the 1 MHz frequency. The temperature dependence of the conductivity exhibits different electrically active states in V2O5/Si and V2O5/FG/Si structures. Thus, the FG layer can modify these states. V2O5 layers with an average film thickness of 1.0-3.6 nm demonstrate the memristive switching with an ON/OFF ratio of ∼1-4 orders of magnitude. At film thicknesses above 5.0 nm, the memristive switching practically vanishes. V2O5 films with an average thickness of 3.6 nm were found to be particularly stable and promising for memristive switching applications.

Ultrafast Infrared Laser Crystallization of Amorphous Si/Ge Multilayer Structures.

Silicon-germanium multilayer structures consisting of alternating Si and Ge amorphous nanolayers were annealed by ultrashort laser pulses at near-infrared (1030 nm) and mid-infrared (1500 nm) wavelengths. In this paper, we investigate the effects of the type of substrate (Si or glass), and the number of laser pulses (single-shot and multi-shot regimes) on the crystallization of the layers. Based on structural Raman spectroscopy analysis, several annealing regimes were revealed depending on laser fluence, including partial or complete crystallization of the components and formation of solid Si-Ge alloys. Conditions for selective crystallization of germanium when Si remains amorphous and there is no intermixing between the Si and Ge layers were found. Femtosecond mid-IR laser annealing appeared to be particularly favorable for such selective crystallization. Similar crystallization regimes were observed for both single-shot and multi-shot conditions, although at lower fluences and with a lower selectivity in the latter case. A theoretical analysis was carried out based on the laser energy absorption mechanisms, thermal stresses, and non-thermal effects.

Visualization of Swift Ion Tracks in Suspended Local Diamondized Few-Layer Graphene.

In the present study we investigated the nanostructuring processes in locally suspended few-layer graphene (FLG) films by irradiation with high energy ions (Xe, 26-167 MeV). For such an energy range, the main channel of energy transfer to FLG is local, short-term excitation of the electronic subsystem. The irradiation doses used in this study are 1 × 1011-5 × 1012 ion/cm2. The structural transformations in the films were identified by Raman spectroscopy and transmission electron microscopy. Two types of nanostructures formed in the FLG films as a result of irradiation were revealed. At low irradiation doses the nanostructures were formed preferably at a certain distance from the ion track and had the form of 15-35 nm "bunches". We assumed that the internal mechanical stress that arises due to the excited atoms ejection from the central track part creates conditions for the nanodiamond formation near the track periphery. Depending on the energy of the irradiating ions, the local restructuring of films at the periphery of the ion tracks can lead either to the formation of nanodiamonds (ND) or to the formation of AA' (or ABC) stacking. The compressive strain value and pressure at the periphery of the ion track were estimated as ~0.15-0.22% and ~0.8-1.2 GPa, respectively. The main novel results are the first visualization of ion tracks in graphene in the form of diamond or diamond-like rings, the determination of the main condition for the diamond formation (the absence of a substrate in combination with high ion energy), and estimates of the local strain at the track periphery. Generally, we have developed a novel material and have found how to control the film properties by introducing regions similar to quantum dots with the diamond interface in FLG films.

Engineering of graphene flakes in the process of synthesis in DC plasma jets.

During the pyrolysis of hydrocarbons in helium plasma jets in a plasma-chemical reactor, graphene flakes of a different structure and resistance were obtained. The presence of hydrogen in these structures was established by physicochemical methods, and its content depends on the pressure in the plasma-chemical reactor and the composition of a plasma-forming system. In addition to hydrogen, a relatively low concentration of oxygen atoms is present in the graphene flakes. Hydrogen is involved in the graphene nucleation, whereas oxygen is absorbed on graphene flakes from the air at low temperatures. It was found that a pressure increase in the reactor (up to 710 Torr) leads to the formation of flakes with a low resistivity (0.12-0.20 kOhm sq-1) and low defect density. In the case of synthesis at a low pressure (350-500 Torr), the resistance of graphene flakes is increased by three orders of magnitude (100-400 kOhm sq-1) with a more complicated defect structure and built-in hydrogen. Moreover, hydrogen is difficult to remove from these flakes, and annealing at relatively high temperatures (up to 300 °C) leads to a weak decrease in the resistance due to flake deformation. Additionally, the functionalization of the graphene flakes synthesized at a low pressure with fluorine atoms is suppressed due to their structural features. In general, the selection of growth parameters (gas pressure in a camera, flow rate and content of impurity atoms) allows one to control the defects in graphene, and its structure and conductivity.

Resistance Switching in Polycrystalline C12A7 Electride.

The memory (memristive) properties of an electride material based on polycrystalline mayenite (C12A7:e-) were studied. The phase composition of the material has been confirmed by such methods as XRD, TEM, Raman, and infrared spectroscopy. The electride state was confirmed by conductivity measurements and EPR using a characteristic signal from F+-like centers, but the peak at 186 cm-1, corresponding to an electride with free electrons, was not observed explicitly in the Raman spectra. The temperature dependence of current-voltage characteristics in states with low and high resistance (LRS and HRS) has been studied. In the LRS state, the temperature dependence of the current has a non-Arrhenius character and is described by the Hurd quantum tunnelling model with a Berthelot temperature of 262 K, while in the HRS state, it can be described in terms of the Arrhenius model. In the latter case, the existence of two conduction regions, "impurity" and "intrinsic", with corresponding activation energies of 25.5 and 40.6 meV, was assumed. The difference in conduction mechanisms is most likely associated with a change in the concentration of free electrons.

Radiation-Stimulated Formation of Two-Dimensional Structures Based on Calcium Silicide.

The formation of CaSi2 polycrystalline structures under the postgrowth electron irradiation of epitaxial CaF2/Si(111) films with embedded thin Si layers was studied. The dependence on the electron exposure time was investigated for two types of structures with different film thicknesses. The optimal conditions for the formation of two-dimensional CaSi2 structures were found. Raman spectra of the structures after a 1 min electron irradiation demonstrated only one pronounced peak corresponding to the vibrations of Si atoms in the plane of the calcium-intercalated two-dimensional Si layer. An increase in the exposure time resulted in the transition from two- to three-dimensional CaSi2 structures having more complex Raman spectra with additional peaks typical of bulk CaSi2 crystals. Based on the results of microscopic studies and transport measurements, a model explaining the observed effects was proposed.

Radiation-Induced Nucleation and Growth of CaSi2 Crystals, Both Directly during the Epitaxial CaF2 Growth and after the CaF2 Film Formation.

The radiation-induced phenomena of CaSi2 crystal growth were investigated, both directly during the epitaxial CaF2 growth on Si (111) and film irradiation with fast electrons on Si (111) after its formation, while maintaining the specified film thickness, substrate temperature and radiation dose. Irradiation in the process of the epitaxial CaF2 film growth leads to the formation of CaSi2 nanowhiskers with an average size of 5 µm oriented along the direction <110>. The electron irradiation of the formed film, under similar conditions, leads to the homogeneous nucleation of CaSi2 crystals and their proliferation as inclusions in the CaF2 film. It is shown that both approaches lead to the formation of CaSi2 crystals of the 3R polymorph in the irradiated region of a 10 nm thick CaF2 layer.

The Influence of Argon Cluster Ion Bombardment on the Characteristics of AlN Films on Glass-Ceramics and Si Substrates.

In this paper, the influence of surface modification on the characteristics and properties of AlN thin films on Si and glass-ceramics substrates is investigated. The surface modification was made at various parameters of argon cluster ions. By using XRD and Raman spectroscopy, it was shown that the obtained AlN films have a hexagonal structure with a characteristic direction of texturing along the c axis and slight deviations from it. A comparison of the AlN surface morphology obtained by atomic force microscopy before and after cluster processing was demonstrated. This demonstrated that the cluster ions with low energy per atom (E/N = 10 eV/atom) have a high efficiency of surface smoothing. A decrease in the intensity of the Raman peaks and an increase in their full-width after bombardment with cluster ions were found, which may be caused by a change in the physicochemical state of the surface. The optical properties, the quality of the boundaries, and the distribution map of the thickness of the functional layer of AlN were investigated by the methods of spectral and spatial resolution ellipsometry. By using the cross-sectional SEM, the direction of crystallite texturing was demonstrated. The influence of argon cluster ion bombardment on the stoichiometry of samples was analyzed by EDX spectroscopy. The results obtained demonstrate the efficiency of the cluster ion smoothing of polycrystalline thin films for microelectronics, particularly when creating surface acoustic wave resonators.

Nanoscale potential fluctuations in nonstoichiometrics tantalum oxide.

The atomic and electronic structure of nonstoichiometric amorphous tantalum oxide (TaO x ) films of different composition has been investigated by means of electron microscopy, x-ray photoelectron spectroscopy, Raman and infrared spectroscopy. The dispersion of the absorption coefficient and refraction index has been studied by spectral ellipsometry. The optical spectra were interpreted using the results of a quantum-chemical simulation for crystalline orthorhombic TaO x . It was found that the presence of oxygen vacancies in the oxygen-deficient TaO x film show an optical absorption peak at 4.6 eV. It has been established that TaO x consists of stoichiometric Ta2O5, metallic Ta clusters less than 20 nm in size, and tantalum suboxides TaO y (y < 2.5). The model of nanoscale potential fluctuations of TaO x bandgap in the range of 0-4.2 eV is proposed and justified. The design of the flash memory element based on the effect of localization of electrons and holes in Ta metallic nanoclusters in the TaO x matrix is proposed.

Tunable properties of few-layer graphene-N-methylpyrrolidone hybrid structures.

A few-layer graphene-based hybrid material with high thermal and chemical stability and reproducible and tunable electronic properties was fabricated by intercalation of N-methylpyrrolidone into a few-layer graphene combined with heat treatment. Depending on the process temperature, the obtained material could be produced with the following properties: a broad range of resistivity values (six to seven orders of magnitude) in combination with a high carrier mobility, a tunable band-gap (from 0 up to 3-4 eV) and sp² or sp³ hybridization of carbon atoms. The extremely strong step-like temperature dependence (within 10 °C) of its properties observed in the vicinity of two temperatures, 90 and 200 °C, seems to be important for various applications. The hybrid material opens viable routes to progress in the design of three-dimensional nanostructures.