Chemical and structural modifications of laser treated iron surfaces: investigation of laser processing parameters

This study focuses on the chemical, morphological and structural characterization of iron surfaces treated by laser in ambient air. Incorporation of nitrogen over a 1–2 μm thickness (10–30 at.% at the profile maximum) and superficial oxidation on 200–400 nm depth have been evidenced by nuclear reaction analyses. X-ray diffraction at grazing incidence has shown the formation of FeO and Fe₃O₄ oxide phases as well as γ-Fe(N), and ε-Fe_xN for a sufficiently high amount of nitrogen incorporated. Treatments performed with different laser beams indicate that the parameter playing the major role in surface modification processes is the wavelength. Nitrogen incorporation has been found to occur via the interaction of reactive N, present in the laser-induced plasma, and the iron molten bath. The nitriding process is promoted in the IR wavelength range. Oxidation takes place by chemical reaction during the cooling step, and is furthered in the case of UV treatment.     

A comparative infrared study of H2O reactivity on Si(1 0 0)-(2 × 1), (2 × 1)-H, (1 × 1)-H and (3 × 1)-H surfaces

The water adsorption on the bare and H-terminated Si(1 0 0) surfaces has been studied by the BML-IRRAS technique. It is found that H-terminated surfaces are much less reactive compared to the bare silicon surfaces. The (1 × 1)-H and (3 × 1)-H surfaces show similar and less reactivity pattern compared to the (2 × 1)-H surface. At higher exposures, the water reaction with coupled monohydride species provides an effective channel for oxygen insertion into the back bonds of dihydride species. It is not attributed to the H–Si–Si–H + H₂O → H–S–Si–OH + H₂, which could give rise to the characteristic Si–H and Si–OH modes, respectively at 2081 and 921 cm⁻¹. A more suitable reaction mechanism involving a metastable species, H–Si–Si–H + H₂O → H₂Si  HO–Si–H (metastable) explains well the bending modes of oxygen inserted silicon dihydride species which are observed relatively strongly in the reaction of water with H-terminated Si(1 0 0) surfaces.     

MBE grown type-II MWIR and LWIR superlattice photodiodes

We report on the status of GaSb/InAs type-II superlattice diodes grown and fabricated at the Jet Propulsion Laboratory designed for infrared absorption 2–5 μm and 8–12 μm bands. Recent LWIR devices have produced detectivities as high as 8 × 10¹⁰ Jones with a differential resistance–area product greater than 6 Ohm cm² at 80 K with a long wavelength cutoff of approximately 12 μm. The measured internal quantum efficiency of these front-side illuminated devices is close to 30% in the 10–11 μm range. MWIR devices have produced detectivities as high as 8 × 10¹³ Jones with a differential resistance–area product greater than 3 × 10⁷ Ohm cm² at 80 K with a long wavelength cutoff of approximately 3.7 μm. The measured internal quantum efficiency of these front-side illuminated MWIR devices is close to 40% in the 2–3 μm range at low temperature and increases to over 60% near room temperature.     

Covalent binding of cyclohexene, 1,3-cyclohexadiene and 1,4-cyclohexadiene on Si(1 1 1)-7 × 7

The adsorption reactions and binding configurations of cyclohexene, 1,3-cyclohexadiene and 1,4-cyclohexadiene on Si(1 1 1)-7 × 7 were studied using high-resolution electron energy loss spectroscopy (HREELS), ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS) and DFT calculation. The covalent attachments of these unsaturated hydrocarbons to Si(1 1 1)-7 × 7 through the formation of Si–C linkages are clearly demonstrated by the observation of the Si–C stretching mode at 450–500 cm⁻¹ in their HREELS spectra. For chemisorbed cyclohexene, the involvement of π_C=C in binding is further supported by the absence of C=C stretching modes and the disappearance of the π_C=C photoemission. The chemisorption of both 1,3-cyclohexadiene and 1,4-cyclohexadiene leads to the formation of cyclohexene-like intermediates through di-σ bonding. The existence of one π_C=C bond in their chemisorbed states is confirmed by the observation of the C=C and (sp²)C---H stretching modes and the UPS and XPS results. DFT calculations show that [4 + 2]-like cycloaddition is thermodynamically preferred for 1,3-cyclohexadiene on Si(1 1 1)-7 × 7, but a [2 + 2]-like reaction mechanism is proposed for the covalent attachment of cyclohexene and 1,4-cyclohexadiene.     

Coating zinc oxide submicron crystals on poly(methyl methacrylate) chips and spheres via ultrasound irradiation

Ultrasound irradiation is used for anchoring zinc oxide submicron crystals with a main diameter and length of 280 nm and 470 nm, respectively, onto the surface of poly(methyl methacrylate) PMMA chips (2 mm diameter), and zinc oxide crystals with a mean diameter and length of 150 nm and 230 nm, respectively, onto the surface of the PMMA spheres (1–10 μm). The zinc oxide crystals were obtained by sonochemical irradiation of a mixture containing the PMMA, zinc (II) acetate dihydrate, ethanol, water, and 24 wt.% aqueous ammonia for 2 h, yielding a PMMA–zinc oxide composite. By controlling the atmosphere and reaction conditions, we could achieve well-adhered zinc oxide crystals on the surface of poly(methyl methacrylate). The resulting zinc oxide–PMMA composite was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray analysis (EDX), high-resolution scanning electron microscopy (HRSEM), and photoluminescence (PL) spectroscopy. The zinc oxide-deposited PMMA chips (loaded with 0.03–1.0 wt.% ZnO) were successfully homogenized in melt by extrusion and then injection molded into small, disc-shaped samples. These samples were analyzed with respect to their directional spectral optical properties in UV, Vis and IR spectroscopy.     

Preparation of tantalum oxide thin films by photo-assisted atomic layer deposition

Tantalum oxide thin films were prepared by photo-assisted atomic layer deposition (Photo-ALD) in the substrate temperature range of 170–400 °C using Ta(OC₂H₅)₅ and H₂O as precursors. The constant growth rates of 0.42 and 0.47 Å per cycle were achieved for the films grown by normal ALD and Photo-ALD, respectively. The increased growth rate in Photo-ALD is probably due to the reactive surface by photon energy and faster surface reaction. In Photo-ALD, however, the constant growth rate started at lower temperature of 30 °C and one cycle time shortened up to 5.7 s than that of normal ALD. The films grown by normal ALD and Photo-ALD were amorphous and very smooth (0.21–0.35 nm) as examined by X-ray diffractometer and atomic force microscopy, respectively. Also, the refractive index was found to be 2.12–2.16 at the substrate temperature of 190–300 °C, similar to that of the film grown by normal ALD. However, the remarkably low leakage current density of 0.6×10⁻⁶ A/cm² to 1×10⁻⁶ A/cm² at applied field of 1 MV/cm is several order of magnitude smaller than that of normal ALD, probably due to the presence of reactive atom species.     

New electroluminescent alternating polyfluorenevinylenes with phenylene and biphenylene segments

The Heck coupling of 9,9-dihexyl-2,7-divinylfluorene with 1,4-dibromobenzene and 4,4′-dibromobiphenyl afforded the alternating polyfluorenevinylenes P1 and P2, respectively. P2 showed lower solubility in common organic solvents, higher thermal stability and slightly higher glass transition temperature than P1. The polymers absorbed around 400 nm, and their optical band gaps were 2.77–2.82 eV. They emitted blue-green light in both solution (emission maximum 451–464 nm, quantum yield 0.52–0.54) and thin film (emission maximum 462–474 nm).     

Performance improvements of ultraviolet/infrared dual-band detectors

Results are reported on dual-band detectors based on a GaN/AlGaN structure operating in both the ultraviolet–midinfrared (UV–MIR) and ultraviolet–farinfrared (UV–FIR) regions. The UV detection is due to an interband process, while the MIR/FIR detection is from free carrier absorption in the emitter/contact followed by internal photoemission over the barrier at the GaN/AlGaN interface. The UV detection, which was observed from 300 K to 4.2 K, has a threshold of 360 nm with a peak responsivity of 0.6 mA/W at 300 K. The detector shows a free carrier IR response in the 3–7 μm range up to 120 K, and an impurity response around 54 μm up to 30 K. A response in the range 7–13 μm, which is tentatively assigned to transitions from C impurities and N vacancies in the barrier region, was also observed. It should also be possible to develop a detector operating in the UV–visible–IR regions by choosing the appropriate material system. A dual-band detector design, which allows not only to measure the two components of the photocurrent generated by UV and IR radiation simultaneously but also to optimize the UV and IR responses independently, is proposed.     

Sonochemical degradation of triclosan in water and wastewater

The sonochemical degradation of 5 μg l⁻¹ triclosan, a priority micro-pollutant, in various environmental samples (seawater, urban runoff and influent domestic wastewater) as well as in model solutions (pure and saline water) was investigated. Experiments were conducted with a horn-type sonicator operating at 80 kHz frequency and a nominal applied power of 135 W, while solid-phase microextraction coupled with gas chromatography–electron capture detector (SPME/GC–ECD) was employed to monitor triclosan degradation. The latter followed pseudo-first order kinetics with the rate constant being (min⁻¹): 0.2284 for seawater > 0.1051 for 3.5% NaCl in deionised water > 0.0597 for centrifuged urban runoff  0.0523 for untreated urban runoff > 0.0272 for deionised water > 0.0063 for wastewater influent. SPME/GC–ECD and SPME coupled with gas chromatography–mass spectrometry (SPME/GC–MS) were also used to check for the formation of chlorinated and other toxic by-products; at the conditions in question, the presence of such compounds was not confirmed.     

The beneficial influence of ultrasound in the polymerization of epsilon-caprolactam to polyamide-6 (Nylon 6). Part II: additional experiment to understand the "pre-sonication effect"

Ultrasound (US) “pre-sonication effect” is the beneficial effect of US in the hydrolytic polymerization of ε-caprolactam (CL) mixtures with very low water concentrations (about 0.1–1 wt%). It appears after a mild initial treatment of the mixtures with US [17.5–20 kHz, short times (5–15 min), low temperatures (70–110 °C)] followed by heating at 220–260 °C. An explanation is proposed on the basis of the formation in mild conditions (100 °C) of low concentrations of cyclic oligomers never detected in the literature at those conditions. These, under US irradiation, produce linear amino acid oligomers, which are strong activators of polymerization when the mixture of CL and water, after US irradiation, is heated at the suitable polymerization temperature indicated above.     

Structural properties of diamond fine particles and clusters prepared by detonation and decomposition of TNT

The thermal parameter B for three different particle sizes of diamond samples (bulk powder 1–4 μm, fine particle 144–195 Å and cluster 55–61 Å) was determined by the grazing incidence X-ray diffraction method. The values of B were found to be in the range 0.50–0.70 Å² for particles in the size range 195–55 Å and 0.27 Å² for 1–4 μm. All of them are larger than that of diamond bulk. A clear size dependence of B, increasing with decreasing particle size, was found. By analysing X-ray diffraction data at several temperatures the magnitude of B was found to be due to B_S (static part) instead of B_T (dynamic part). The average B_S values obtained were 0.04 Å², 0.19 Å² and 0.27 Å² for bulk powder, fine particle and cluster samples respectively. Ultrahigh resolution transmission electron microscope (TEM) observation confirmed the presence of strain, distortion, roughness and dislocation lines in many particles. TEM images of particles indicate that the clusters were not spherical in shape; they were mostly cubiform and some were truncated prism-like polyhedral. The present study reveals that the B_S component is responsible for the large B value in diamond fine particles and clusters. No clear surface local atomic distortion was found in the particles.     

640 × 512 pixel narrow-band, four-band, and broad-band quantum well infrared photodetector focal plane arrays

A 9 μm cutoff 640 × 512 pixel hand-held quantum well infrared photodetector (QWIP) camera has been demonstrated with excellent imagery. A noise equivalent differential temperature (NEDT) of 10.6 mK is expected at a 65 K operating temperature with f/2 optics at a 300 K background. This focal plane array has shown background limited performance at a 72 K operating temperature with the same optics and background conditions. In this paper, we discuss the development of this very sensitive long-wavelength infrared camera based on a GaAs/AlGaAs QWIP focal plane array and its performance in quantum efficiency, NEDT, uniformity, and operability. In the second section of this paper, we discuss the first demonstration of a monolithic spatially separated four-band 640 × 512 pixel QWIP focal plane array and its performance. The four spectral bands cover 4–5.5, 8.5–10, 10–12, and 13.5–15 μm spectral regions with 640 × 128 pixels in each band. In the last section, we discuss the array performance of a 640 × 512 pixel broad-band (10–16 μm full-width at half-maximum) QWIP focal plane.     

DFT modeling of the hydrolysis of isocyanic acid over the TiO2 anatase (1 0 1) surface: Adsorption of HNCO species

The nature of the interaction of isocyanic acid (HNCO) with the active centers at the ideal anatase TiO₂ (1 0 1) surface were studied using ab initio density functional theory (DFT) method with a cluster model. Two types of adsorption of isocyanic acid are found to be likely at (1 0 1) surface – dissociative and molecular adsorption. Only molecular adsorption of HNCO leads to the direct weakening and further splitting of the NC bond, which is a necessary step for the hydrolysis of isocyanic acid. During molecular adsorption of HNCO, an energetically stable intermediate surface complex is created with an adsorption energy of −1.33 eV, in which the HNCO skeleton is changing due to new strong bonds between C–O_s and N–Ti_s. Based on the existence of this intermediate complex a probable reaction pathway for the hydrolysis of HNCO over the ideal anatase (1 0 1) surface was developed. A surface oxygen vacancy was formed after the decomposition of the intermediate complex and CO₂ desorption. Afterwards, water adsorbs at the oxygen vacancy site and NH₃ is successively formed. The HNCO hydrolysis over TiO₂ was found to be energetically favorable with global energy gain of about −2.08 eV.     

Effect of oxide thickness on the capacitance and conductance characteristics of MOS structures

In this work, the investigation of the interface states density and series resistance from capacitance–voltage (C–V) and conductance–voltage (G–V) characteristics in Au/SnO₂/n-Si (MOS) structures prepared at various SnO₂ layer thicknesses by spray deposition technique have been reported. It is fabricated five samples depending on deposition time. The thicknesses of SnO₂ films obtained from the measurement of the oxide capacitance in the strong accumulation region for MOS Schottky diodes are 37, 79, 274, 401, and 446 Å, for D1, D2, D3, D4, and D5 samples, respectively. The C–V and G–V measurements of Au/SnO₂/n-Si MOS structures are performed in the voltage range from −6 to +10 V and the frequency range from 500 Hz to 10 MHz at room temperature. It is observed that peaks in the forward C–V characteristics appeared because of the series resistance. It has been seen that the value of the series resistance R_s of samples D1 (47 Ω), D2 (64 Ω), D3 (98 Ω), D4 (151 Ω), and D5 (163 Ω) increases with increasing the oxide layer thickness. The interface state density D_it ranges from 2.40×10¹³ cm⁻² eV⁻¹ for D1 sample to 2.73×10¹² cm⁻² eV⁻¹ for D5 sample and increases with increasing the oxide layer thickness.     

Effect of Cu doping in MgB2 superconductor at various processing temperatures

The effects of Cu doping in MgB₂ superconductor has been studied at different processing temperatures. The polycrystalline samples of Mg_1−xCu_xB₂ with x = 0.05 were synthesized through the in-situ solid sate reaction method in argon atmosphere at different temperature range between 800–900 °C. The samples were characterized through X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and low temperature R–T measurement techniques for the phase verification, microstructure and superconducting transition temperature, respectively. The XRD patterns of Mg_1−xCu_xB₂ (x = 0.05) do not exhibit any impurity traces of MgB₄ or MgB₆ and they show the sharp transition in the samples prepared at 850 °C. The onset transition temperature of the prepared samples is around 39 K, which is almost the same as that for the pure MgB₂. This indicates that Cu doping in MgB₂ does not affect the transition temperature. The SEM micrograph of Mg_0.95Cu_0.05B₂ has shown that the sample is dense with grain size smaller than 1 μm.     

Method for independent control of particle size and distance in rhodium epitaxy on TiO2(110)-(1×2) surface An STM study

A method for independent control of the particle size and distance is presented for rhodium epitaxy on TiO₂(110)-(1×2) surface. The real space imaging of the surface morphology was performed by scanning tunneling microscopy. The amount of the deposited rhodium was checked by Auger electron spectrometry. The method consists of two steps: (i) evaporation of 0.001–0.050 ML equivalent of rhodium at room temperature with a post-annealing at 1100 K (“seeding”); (ii) post-deposition of rhodium for growing of the Rh nanoparticles formed in step (i) (“growing”). The mechanism of this procedure is based on the large difference of the surface diffusion coefficient between Rh adatoms and Rh nanocrystallites larger than 1–2 nm. In the first step the average distance between the metal particles is controlled in the range 5–200 nm, the second step determines the particles size (2–50 nm). This work demonstrates that the diffusion processes of metal nanoparticles of different sizes and the growing modes of the crystallites can be studied in detail by application of seeded surfaces.     

A metastable de-excitation spectroscopy (MDS) study on oxygen adsorption on a polycrystalline zirconium surface

The adsorption of oxygen on a polycrystalline zirconium surface at room temperature has been studied by metastable de-excitation spectroscopy (MDS) in conjunction with UPS and AES. From the analysis of the measured spectra, we have shown the following. (1) At the initial stage of oxygen adsorption (exposure <1.2 L), the surface density of states (SDOS) of zirconium changes little at around the Fermi level (E_F), while it decreases appreciably at 1–2 eV below E_F (E_B=1–2 eV) by oxygen adsorption. (2) The SDOS at E_B=0–2 eV decreases with increasing oxygen exposure at >1.2 L and disappears at >8 L. (3) The oxygen 2p states (E_B=5–8 eV) are localized at the subsurface region at oxygen exposure 0–2 L. (4) The ZrO₂ phase appears at the outermost zirconium surface at around 2 L, then grows with increasing exposure, and finally dominates at >8 L. It is suggested that two different phases (ZrO₂ phase and that in which oxygen occupies subsurface sites) coexist at the outermost surface at 2–8 L.     

Magnetic properties of Sm–Co–B-based nanocomposite magnets

The magnetic properties of nanocomposite melt-spun magnets with composition Sm_16−xCo_68+xB₁₆ (x=0–10, 2 at% interval) and Sm₈Co_92−yB_y (y=10–18, 2 at% interval) have been studied systematically. Several ribbons were fabricated with a wheel speed of 50 m/s, followed by annealing in the temperature range of 700–800°C for 2.5–40 min. XRD results and magnetization versus temperature curves showed that almost all of the samples were composed of the tetragonal Sm₂Co₁₄B and rhombohedral SmCo₁₂B₆ phases which are not magnetically hard at room temperature. However, a relatively high coercivity in the range of 3.5–5.5 kOe has been obtained in these samples. The highest coercivity of 5.5 kOe and a very promising β value of −0.28%/°C were obtained in Sm₈Co₇₄B₁₈ ribbons annealed at 750°C for 5 min. The high coercivities are attributed to the small grain size of the 2 : 14 : 1 phase, in which the large surface areas enhance its effective anisotropy, and make it uniaxial type.     

Femtosecond laser spectroscopy of In0.53Ga0.47As/InP multiple quantum wells: interfacial roughness and photoexcited carrier relaxation

Interfacial properties and relaxation dynamics of photoexcited carriers in In_0.53Ga_0.47As/InP multiple quantum wells (MQWs) have been investigated by means of cross-sectional scanning tunneling spectroscopy and optical spectroscopy methods (luminescence, absorption and pump–probe experiments). The MQW structure consists of 125 periods of 10-nm-wide well layers and 40-nm-wide barrier layers on an InP(0 0 1) substrate. The observed interfacial roughness of the InGaAs-on-InP is 1–2 monolayers (ML), while that of the InP-on-InGaAs is 3–4 ML. The Stokes shift observed in luminescence and absorption spectra at 77 K corresponds well to the well-width distribution observed by the cross-sectional STM. Differential absorption spectra measured by pump–probe spectroscopy show that relaxation of hot carriers in conduction and valence bands followed by exciton formation takes place in 17–30 ps depending on the excitation photon energy. The excitons formed at the band bottom are localized at thicker areas within a quantum well in 500 ps.     

The effects of a trace addition of silver upon elevated temperature ageing of an Al–Zn–Mg alloy

Microalloying additions of Ag (0.1 at.%) increase the hardening response of Al–Zn–Mg alloys to elevated temperature ageing in the range 100–200°C due to the formation of a high density of very fine η′ precipitate plates. The present study employed transmission electron microscopy (TEM) and three-dimension atom probe (3DAP) to study the early stages of ageing in the alloy Al–1.8Zn–3.4Mg–0.1Ag (at.%) in an attempt to identify the role of Ag in stimulating precipitation hardening. During isothermal ageing at 90°C, the hardening response is attributed to a high density of Zn–Mg–Ag rich solute clusters and GP zones. During ageing at 150°C, η′ precipitates nucleate at Zn–Mg–Ag rich solute clusters, the former growing as {111} platelets with an average composition of approximately 20 at.% Zn, 20 at.% Mg and 1.4 at.% Ag. The 3DAP data indicates that the co-segregation of Zn and Ag and subsequently Zn and Mg atoms precedes the formation of the Zn–Mg–Ag rich solute clusters. The GP zones and η′ precipitates were observed to possess a Zn:Mg ratio close to 1:1, whereas the equilibrium η precipitates possessed compositions consistent with MgZn₂. Furthermore, partitioning of Ag was observed inside all precipitate phases, viz. G.P. zones, η′ and η.