Effect of the pulsed laser deposition conditions on the tribological properties of thin-film nanostructured coatings based on molybdenum diselenide and carbon

The structural state and tribological properties of gradient and composite antifriction coatings produced by pulsed laser codeposition from MoSe₂(Ni) and graphite targets are studied. The coatings are deposited onto steel substrates in vacuum and an inert gas, and an antidrop shield is used to prevent the deposition of micron-size particles from a laser jet onto the coating. The deposition of a laser jet from the graphite target and the application of a negative potential to the substrate ensure additional high-energy atom bombardment of growing coatings. Comparative tribological tests performed at a relative air humidity of ∼50% demonstrate that the “drop-free” deposition of a laser-induced atomic flux in the shield shadow significantly improves the antifriction properties of MoSe _x coatings, decreasing the friction coefficient from 0.07 to 0.04. The best tribological properties, which combine a low friction coefficient and high wear resistance, are detected in drop-free MoSe _x coatings additionally alloyed with carbon (up to ∼55 at %) and subjected to effective bombardment by high-energy atoms during growth. Under these conditions, a dense nanocomposite structure containing the self-lubricating MoSe₂ phase and an amorphous carbon phase with a rather high concentration of diamond bonds forms.     

Pulsed laser deposition of BaGa<Subscript>2</Subscript>O<Subscript>4</Subscript>

This paper reports the first results obtained on monobarium gallate thin films grown on silicon and platinum coated substrates by pulsed laser deposition. The influence of oxygen background pressure and substrate (or post-annealing) temperature on the film properties was studied. The films were characterized by XRD, RHEED, AFM, photoelectron and electrical impedance spectroscopy. The structure analysis showed that the films crystallized into a hexagonal phase, most probably into (metastable) α-BaGa₂O₄. Depending on deposition conditions, films with different (from nearly epitaxial to polycrystalline) textures were obtained.     

Growth and thermoelectric properties of FeSb<Subscript>2</Subscript> films produced by pulsed laser deposition

Thermoelectric FeSb₂ films were produced by pulsed laser deposition on silica substrates in a low-pressure Ar environment. The growth conditions for near phase-pure FeSb₂ films were confirmed to be optimized at a substrate temperature of 425°C, an Ar pressure of 2 Pa, and deposition time of 3 h by ablating specifically prepared compound targets made of Fe and Sb powders in atomic ratio of 1:4. The thermoelectric transport properties of FeSb₂ films were investigated. Pulsed laser deposition was demonstrated as a method for production of good-quality FeSb₂ films.     

Pulsed laser deposition of thin-film coatings using an antidroplet shield

The formation of thin-film coatings of molybdenum diselenide is studied during the deposition of a laser-induced material flux using a shield that is placed on the path of the expansion of this flux in order to trap the droplet fraction. To increase the efficiency of atomic scattering into the shadow zone (behind the shield), deposition is carried out in an inert gas (argon). As the argon pressure increases to 2 Pa, low-density coatings with a developed surface relief form in the shadow zone. When a negative bias voltage is applied to a substrate, the quality of the coating increases substantially. Numerical experiments based on the combination of two computer models that describe physical processes on the atomic level using Monte Carlo methods are performed to reveal the factors that affect the thickness, chemical composition, and structure of the MoSe _x coatings deposited in the shadow zone. The results of calculating the dynamics of the laser-induced atomic flux in a chamber with a shield are used to simulate the coating growth. The deposition of a scattered atomic flux under conditions of surface bombardment by incident particles is shown to substantially increase the coating density and to smooth away the surface relief.     

Evolution of elemental distribution in free-standing structures of Zr/ZrSi<Subscript>2</Subscript> with MoSi<Subscript>2</Subscript> and ZrSi<Subscript>2</Subscript> protective coatings under annealing

An analysis of the in-depth distribution of elements in annealed samples of multilayer Zr/ZrSi₂ EUV filters with protective layers of MoSi₂ and ZrSi₂ was performed by secondary ion mass spectrometry (SIMS). The vacuum annealing of the samples was performed at temperatures of up to 720–950°C for 3–7 h and at a residual pressure of ∼10⁻⁷ torr. It was demonstrated that MoSi₂ coatings effectively inhibit the accumulation of oxygen by the heated film, which is the process that determines the optical degradation of the filter.     

Study of shock waves interacting with Ar and N<Subscript>2</Subscript> low pressure dc discharges

Acoustical shock waves (Mach number <2) generated in situ by spark gap are propagated in weakly ionized dc discharges working at low pressure (399 Pa) and containing either Ar or N₂ gas. The electrical characterization and the laser deflection technique are used to measure the characteristics of dc discharge (such as voltage, resistance and power of discharge) and the structure and velocity of shock wave, respectively. The results stress the importance of atomic and molecular nature of the gases in affecting the power deposition and the shock wave properties.     

Factors affecting the superconductivity in the process of depositing Nd1.85Ce0.15CuO4-δ by the pulsed electron deposition technique

On SrTiO₃ single crystal substrate, by using the pulsed electron deposition technique, the high-quality electron doped Nd_1.85Ce_0.15CuO_4−δ superconducting film was successfully fabricated. After careful study on the R-T curves of the obtained samples deposited with different substrate temperatures, thicknesses, annealing methods and pulse frequencies, the effects of them on the superconductivity of the films were found, and the reasons were also analyzed. Additionally, by using the same model of the pulsed laser deposition technique, the relation between the target-to-substrate distance and the deposition pressure was drawn out as a quantitative one. Supported by the Key Project of Zhejiang Provincial Natural Science Foundation (Grant No. Z605131), the ‘100 Talents Project’ of Chinese Academy of Sciences, the Creative Research Group of National Natural Science Foundation of China (Grant No. 60321001) and the National Natural Science Foundation of China (Grant No. 60571029)     

Frustrated exchange interactions formation at low temperatures and high hydrostatic pressures in La<Subscript>0.70</Subscript>Sr<Subscript>0.30</Subscript>Mn<Subscript>O2.85</Subscript>

The magnetic and thermal properties of the anion-deficient La_0.70Sr_0.30MnO_2.85 manganite are investigated in wide temperature (4–350 K) range, including under hydrostatic pressure (0–1.1 GPa). Throughout the pressure range investigated, the sample is spin glass with diffused phase transition into paramagnetic state. It is established, that spin glass state is a consequence of exchange interaction frustration of the ferromagnetic clusters embeded into antiferromagnetic clusters. The magnetic moment freezing temperature T _f of ferromagnetic clusters increases under pressure, freezing temperature dependence on pressure is characterized by derivative value ∼4.5 K/GPa, while the magnetic ordering T _MO temperature dependence is characterized by derivative value ∼13 K/GPa. The volume fraction of sample having ferromagnetic state is V _fer ∼ 13% and it increases under a pressure of 1.1 GPa by ΔV _fer ≈ 6%. Intensification of ferromagnetic properties of the anion-deficient La_0.70Sr_0.30MnO_2.85 manganite under hydrostatic pressure is a consequence of oxygen vacancies redistribution and unit cell parameters decrease. The most likely mechanism of frustrated exchange interactions formation is discussed.     

The effect of argon gas pressure on structural,morphological and photoluminescence properties of pulsed laser deposited KY<Subscript>3</Subscript>F<Subscript>10</Subscript>:Ho<Superscript>3+</Superscript> thin films

KY₃F₁₀:Ho³⁺ thin films were deposited by a pulsed laser deposition technique with Nd–YAG laser radiation (λ = 266 nm) on (100) silicon substrate. The XRD and FE-SEM results show improved crystalline structure for the film deposited at a pressure of 1 Torr. The AFM results show that the RMS roughness of the films increases with rise in argon gas pressure. The EDS elemental mapping shows Y-excess for all the films deposited under all pressures, and this is attributed to its higher mass and low volatility as compared to K and F. XPS analysis further confirmed Y-excess in the deposited films. Green PL emission at 540 nm was investigated at three main excitation wavelengths, namely 362, 416 and 454 nm. The PL emission peaks increase with rise in background argon gas pressure for all excitation wavelengths. The highest PL intensity occurred at excitation of 454 nm for all the thin films. In addition, faint red (near infrared) emission was observed at 750 nm for all the excitations. The green emission at 540 nm is ascribed to the ⁵F₄–⁵I₈ and ⁵S₂–⁵I₈ transitions, and the faint red emission at 750 nm is due to the ⁵F₄–⁵I₇ and ⁵S₂–⁵I₇ transitions of Ho³⁺.     

Effect of plasma spraying regimes on structure and properties of Ni<Subscript>3</Subscript>Al coatings

The structure and tribological properties of coatings made of PN85YU15 powder were studied. The coatings were deposited on the mild steel blanks by the technology of air-plasma spraying using a unit of annular input and gas-dynamic powder focusing. Efficiency of heating and acceleration of powder particles was studied preliminarily. Measurement results on temperature and velocity distributions of particles at a certain spraying distance by the method of spectral pyrometry and time-of-flight method are presented. The effect of plasmatorch arc current and amount of propane-butane in the plasma flow on the structure and properties of coatings is analyzed in this paper. It is determined that the phase composition of coatings and initial powder is the same: the main phase is Ni₃Al compound; moreover, the structure contains Ni₅Al₃ phase. It is shown that an increase in the amount of propane-butane increases coatings porosity. The densest coatings (5.77%) were obtained at the plasmatorch arc current of 200 A with the reduced amount of propane-butane. The coatings obtained at the minimal arc current of 100 A with an increased amount of propane-butane are characterized by maximal porosity (20.38%). The results of tribological testing of the coatings under the conditions of sliding friction with a lubricant by the disc-plane scheme are presented. From the standpoint of obtaining the densest coatings with high performance, the optimal regimes of plasma spraying of PN85YU15 powder are the current from 140 A to 200 and using the air and propane-butane mixture only as the shielding gas (anode curtain).     

InTaO<Subscript>4</Subscript>-based nanostructures synthesized by reactive pulsed laser ablation

Nanostructured Ni-doped indium–tantalum–oxides (InTaO₄) were synthesized by a reactive pulsed laser ablation process, aiming at the final goal of direct splitting of water under visible sunbeam irradiation. The third harmonics beam of a Nd:YAG laser was focused onto a sintered In_0.9Ni_0.1TaO_4−δ target in pure oxygen background gases (0.05–1.00 Torr). Increasing the oxygen gas pressure, via thin films having nanometer-sized strong morphologies, single-crystalline nanoparticles were synthesized in the reactive vapor phases. The nanostructured deposited materials have the monoclinic layered wolframite-type structure of bulk InTaO₄, without oxygen deficiency.     

Carbon-free SiO<Subscript>x</Subscript> films deposited from octamethylcyclotetrasiloxane (OMCTS) by an atmospheric pressure plasma jet (APPJ)

The deposition of carbon-free, silicon oxide (SiO_x) films with a non-thermal, RF capillary jet at 27.12 MHz at normal pressure is demonstrated. The gas mixture for film deposition is constituted of argon, oxygen and small admixtures of octamethylcyclotetrasiloxane (Si₄O₄C₈H₂₄, 0.4 ppm). Surface analysis of the deposited films reveals their exceptionally low carbon content. The XPS atom percentage stays at 2% and less, which is near detection limit. The parametric study reported here focuses on the optimization of the deposition process with regard to the chemical and morphological surface properties of the coating by varying oxygen feed gas concentration (0–0.2%) and substrate temperature (10–50 °C).     

Gradient multilayer tribilogical coatings based on Mo–S–Ti–C formed by hybrid ion-plasma methods

Mechanical, physical and tribological properties of layer-gradient multi-component coatings based on the Mo–S–Ti–C composition are investigated. The coatings are formed by combining the magnetron sputtering and the hybrid magnetron and vacuum arc deposition assisted by a gas plasma generator. A correlation is established between the physic mechanical and tribological properties of the resulting coatings, which allows identifying their potential applications. The physical principles of the combined technologies of lowtemperature ion-plasma deposition of tribological Mo–S–Ti–C coatings onto hardened steel machine parts are developed.     

Microstructural evolution and electrical properties of La<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> thin films grown on SrTiO<Subscript>3</Subscript> substrates by excimer-laser assisted metal-organic deposition

Thin films of La_0.7Ca_0.3MnO₃ were successfully grown epitaxially on (100) single-crystal SrTiO₃ substrates by excimer-laser assisted metal-organic deposition. Initial amorphous LCMO thin films were obtained by metal-organic deposition at 500 °C. Crystallization and epitaxial growth of the films was achieved using a KrF pulsed laser irradiation while the film/substrate samples were kept at 500 °C. High resolution transmission electron microscopy observations on cross-sections demonstrate the formation mechanism of the epitaxial films. The crystallization process starts at the LCMO/STO interface and grows by increasing the number of laser shots. A fully crystallized film was obtained after 5 min of irradiation. The film/substrate interface was found to be sharp and abrupt. The temperature dependence of the resistance R(T) shows various behaviors, starting from insulating to semiconducting and metal–insulator transition material during the formation of the manganite film. The oxygen content was also improved by increasing the irradiation time. Promising values of the temperature coefficient of resistance were obtained from these manganite films for prospect integration in silicon based microbolometric devices. PACS 81.15.-z; 81.15.Np; 73.61.-r; 71.30.+h     

PLD and RF-PLD synthesis of Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>TiO<Subscript>3</Subscript> ferroelectric thin films for electrically controlled devices

Ba_0.6Sr_0.4TiO₃ (BST) bulk ceramic synthesized by solid state reaction was used as target for thin films grown by pulsed laser deposition (PLD) and radiofrequency beam assisted PLD (RF-PLD). The X-ray diffraction patterns indicate that the films exhibit a polycrystalline cubic structure with a distorted unit cell. Scanning Electron Microscopy investigations showed a columnar microstructure with size of spherical grains up to 150 nm. The capacitance–voltage (C–V) characteristics of the BST films were performed by applying a DC voltage up to 5 V. A value of 280 for dielectric constant and 12.5% electrical tunability of the BST capacitor have been measured at room temperature.     

Synthesis and characterization of single crystalline SnO<Subscript>2</Subscript> nanorods by high-pressure pulsed laser deposition

Tin oxide (SnO₂) nanorods were grown by high-pressure pulsed laser deposition (PLD). The nanorods were grown without the use of a catalyst but required high background pressure growth in order to realize small grain columnar growth and nanorod formation, with nanorod formation most favored on non-epitaxial substrates. The structures and morphology were characterized by field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM). X-ray diffraction and HRTEM analysis indicate that the as-grown SnO₂ nanorods are single crystals with a rutile structure. The nanorods are approximately 50–90 nm in diameters and 1.5 μm in length. This method provides an approach for large area synthesis of one dimensional SnO₂ nanostructure materials. PACS 81.16.Mk; 61.46.-w; 81.07.-b     

Metallic liquid hydrogen and likely Al<Subscript>2</Subscript>O<Subscript>3</Subscript> metallic glass

Dynamic compression has been used to synthesize liquid metallic hydrogen at 140 GPa (1.4 million bar) and experimental data and theory predict Al₂O₃ might be a metallic glass at ∼ 300 GPa. The mechanism of metallization in both cases is probably a Mott-like transition. The strength of sapphire causes shock dissipation to be split differently in the strong solid and soft fluid. Once the 4.5-eV H-H and Al-O bonds are broken at sufficiently high pressures in liquid H₂ and in sapphire (single-crystal Al₂O₃), electrons are delocalized, which leads to formation of energy bands in fluid H and probably in amorphous Al₂O₃. The high strength of sapphire causes shock dissipation to be absorbed primarily in entropy up to ∼400 GPa, which also causes the 300-K isotherm and Hugoniot to be virtually coincident in this pressure range. Above ∼400 GPa shock dissipation must go primarily into temperature, which is observed experimentally as a rapid increase in shock pressure above ∼400 GPa. The metallization of glassy Al₂O₃, if verified, is expected to be general in strong oxide insulators. Implications for Super Earths are discussed.     

Yield of singlet oxygen from optically pumped CCl<Subscript>4</Subscript> solution of fullerenes

Boiling occurs in a solution of oxygen and fullerenes in CCl₄ upon optical pumping of C₆₀ upon the fast appearance of incandescent fullerenes in cold solvent. Upon single-photon absorption, a spherical zone of the critical state of CCl₄ is formed within 5 ns (with a diameter of 22–25 nm, P _cr ∼ 45 atm, and T _cr ∼ 556 K). This spherical zone (gas-bubble nucleus) expands to a diameter of ∼100–400 nm for 2–5 ns. If the external pressure (natural or artificial) is rapidly released, the bubble accelerates and emerges into a vacuum chamber within 0.7–25 μs (the length of the passage is 0.1–5 cm depending on the construction of the singlet oxygen generator). We note that singlet oxygen appears 50 ns after the absorption of a photon by fullerene (i.e., inside of the almost formed gas bubble that only begins to emerge from the liquid to a low-pressure gas region).     

Post-deposition processes for nanostructures formed by electron beam induced deposition with Pt(PF<Subscript>3</Subscript>)<Subscript>4</Subscript> precursor

Electron beam induced deposition was performed using a Pt(PF₃)₄ precursor gas. Self-standing nanowires were produced on the edge of a molybdenum film, followed by two post-deposition processes; electron beam irradiation at room temperature and heating at about 400 K in vacuum. The as-deposited nanowires were composed of an amorphous phase, of which the dominant composition was platinum but containing a small amount of phosphorus impurity. After irradiating with a 300 keV electron beam, the amorphous nanowires were transformed to crystalline ones. By heating, the as-deposited nanowires became single-crystal platinum with a large grain size and the phosphorus content disappeared.     

Measurement of the <Superscript>13</Superscript>CO<Subscript>2</Subscript>/<Superscript>12</Superscript>CO<Subscript>2</Subscript> concentration ratio in exhaled air by diode laser spectroscopy

A method for determining the relative concentration of ¹³C/₁₂C isotopes by the vibrational-rotational spectrum of CO₂ molecule absorption in the range near 2 μm was proposed. The use of the entire region of the diode laser tuning (∼7 cm⁻¹) and multivariate linear regression for spectrum approximation allow measurements at atmospheric pressure. The laser frequency is additionally stabilized by injection current variation. The ultimate sensitivity of the setup, determined by the plot of the squared Alan variance, is 0.03% for 2-min signal acquisition. The system does not contain elements cooled by liquid nitrogen and can be used in medical diagnostics.