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At least 1,783 records · Page 99

High-throughput investigation of structural evolution upon solid-state in Cu–Cr–Co combinatorial multilayer thin-film

Cu-Cr-Co combinatorial multilayer thin-films were prepared by a high-throughput ion beam sputtering system. Based on the thickness ratio among the individual nanoscale monolayers (Cu, Cr, Co), the resulting stoichiometry covered the entire phase diagram. The chemical composition and structure of Cu-Cr-Co combinatorial chip upon solid-state reaction were studied by lab-based micro-X-ray fluorescence (mu-XRF) and high-throughput synchrotron X-ray diffraction (XRD), respectively. A composition-structure map for Cu-Cr-Co combinatorial chip was developed through automated data analysis employing hierarchical clustering techniques. The structural evolution of Cu-Cr-Co combinatorial chip as a function of heat-treatment temperature, time, and modulation period were studied systematically. Furthermore, the effect of the elemental distribution in-depth direction was investigated to gain more insights regarding phase transformation. This work provides an efficient method and new perspectives for the design and optimization of the composition and structure of high-performance thin-films.

36 MATERIALS SCIENCE↗

Magnetic properties of high Li doped ZnO sol–gel thin films

Highlights: • Ferromagnetism in high Li doped ZnO films. • Magnetic properties observed by Guoy's and VSM method. • The rod and wrinkle like structures are observed from the surface of the films. • Band gap of ZnO does not get altered by high Li doping. - Abstract: Undoped and Li doped ZnO thin films were deposited on a glass substrate using the sol–gel dip coating method. The films were prepared at 5 mol.% and 10 mol.% of Li doped ZnO at 550 °C annealing temperature and the deposited films were characterized by X-ray diffraction (XRD), microscopic studies, Gouy's method, vibrating sample magnetometer (VSM) and UV–visible spectroscopy. All the deposited thin films had a hexagonal wurtzite structure with polycrystalline grains at random. Primarily magnetic properties of pure and Li doped ZnO films were observed by Guoy's method which depicted Dia and Para magnetic behavior at room temperature. VSM measurement reveals a coercivity of 97.7 Oe in the films. An inverse relative ferromagnetism was perceived in Li doped ZnO films which had an average transmission of <90%.

36 MATERIALS SCIENCE↗

Investigation of structural, optical, electrical and dielectric properties of catalytic sprayed hausmannite thin film

Hausmannite Mn{sub 3}O{sub 4} thin film have been synthesized using spray pyrolysis method. These films are characterized using X-ray diffraction (XRD), atomic force microscope AFM, UV–vis–NIR spectroscopy and impedance spectroscopy. XRD study confirms the tetragonal structure of the as-deposited films with lattice parameters, a = 5.1822 Å and c = 9.4563 Å and a grain size of about 56 nm. UV–vis–NIR spectroscopy was further used to estimate optical constants such as extinction coefficient, refractive index, band gap and Urbach energy. Moreover, impedance spectroscopy analysis was employed to estimate electrical and dielectrical properties of the sprayed thin films. The activation energy values deduced from DC conductivity and relaxation frequency were almost the same, revealing that the transport phenomena is thermally activated by hopping between localized states. The AC conductivity is found to be proportional to ω{sup s}. The temperature dependence of the AC conductivity and the frequency exponent, s was reasonably well interpreted in terms of the correlated barrier-hopping CBH model. The dielectric properties were sensitive to temperature and frequency. The study of the electrical modulus indicated that the charge carrier was localized. Experimental results concerning optical constants as Urbach energy, dielectric constant, electric modulus and AC and DC conductivity were discussed in terms of the hopping model as suggested by Elliott.

36 MATERIALS SCIENCE↗

Effects of cation compositions on the electronic properties and optical dispersion of indium zinc tin oxide thin films by electron spectroscopy

Highlights: • REELS analysis can provide optical dispersion and electronic properties of oxide materials. • The band gap varied with In/Zn/Sn compositions and increased after annealing. • The optical properties were examined using REELS in conjunction with the Tougaard–Yubero model. • The dispersion parameters were determined by a single-oscillator Wemple–DiDomenico model. • The Zn and Sn contents play a crucial role in determining the single-oscillator constant and dispersion energy of IZTO thin films. - Abstract: The electronic properties and optical dispersion of indium zinc tin oxide (IZTO) films with different cation compositions were investigated by reflection electron energy loss spectroscopy (REELS). The REELS spectra of IZTO films revealed that the band gap varied with different Sn/Zn ratios and In content. The optical properties were examined with REELS data using Tougaard–Yubero model and the results were compared with the envelope of the transmission spectra obtained using a UV-spectrometer. The dispersion behavior of the refractive index from REELS results was studied in terms of the single-oscillator Wemple–DiDomenico model. The results showed that the different compositions of In/Zn/Sn caused a change in the dispersion parameters of IZTO thin films in contrast to the static values of refractive indices and dielectric constant which remained the same. Our work demonstrated that REELS is an efficient tool to study the optical properties of a material by obtaining the optical parameters.

36 MATERIALS SCIENCE↗

The role of cobalt doping on magnetic and optical properties of indium oxide nanostructured thin film prepared by sol–gel method

Highlights: • Cobalt doped indium oxide thin films have been prepared by a sol–gel method. • The films have a thickness less than 100 nm and grain size less than 10 nm. • The lattice parameters and grain size of films decrease as Co content increase. • The optical band gap of films increases as the grain size decrease. • The films' magnetic behaviour is sensitive to ratio of oxygen defects per Co ions. - Abstract: The effect of Co doping concentration, (x = 0.025–0.2), in In{sub 2−x}Co{sub x}O{sub 3} thin film was investigated by X-rays diffraction (XRD), transmission electron microscopy, X-ray photoelectron spectroscopy (XPS), Ultraviolet visible spectrophotometer (UV–vis) and vibrating sample magnetometer (VSM). All films were prepared by sol–gel technique followed by spin coating process. The XRD and XPS measurements indicate that Co{sup +2} has been successfully substituted in In{sup +3} site. The TEM measurement shows nanostructure morphology of the films. The doping of Co in indium oxide resulted in a decrease in the lattice parameters and grain size while the band gap increased with increasing Co concentration. Further, by comparing VSM and XPS results, the magnetic behaviour of the films were found to be sensitive to Co concentrations, oxygen vacancies and ratio of oxygen defects to Co concentrations. The magnetic behaviour of the prepared films was explained using bound magnetic polaron (BMP) model.

36 MATERIALS SCIENCE↗

Resistive switching: An investigation of the bipolar–unipolar transition in Co-doped ZnO thin films

Highlights: • A purely bipolar behavior on a Co-doped ZnO thin film has been demonstrated. • We have shown what can happen if a unipolar test is performed in a purely bipolar device. • An explanation for how a sample can show a purely bipolar switching behavior was suggested. • An important open issue about resistive switching effect was put in debate. - Abstract: In order to investigate the resistive switching effect we built devices in a planar structure in which two Al contacts were deposited on the top of the film and separated by a small gap using a shadow mask. Therefore, two samples of 10% Co-doped ZnO thin films were sputtered on glass substrate. High resolution X-ray diffraction (HRXRD) revealed a highly c-axis oriented crystalline structure, without secondary phase. The high resolution scanning electron microscopy (HRSEM) showed a flat surface with good coverage and thickness about 300 nm. A Keithley 2425 semiconductor characterization system was used to perform the resistive switching tests in the bipolar and unipolar modes. Considering only the effect of compliance current (CC), the devices showed a purely bipolar behavior since an increase in CC did not induce a transition to unipolar behavior.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Synthesis, characterization and optical properties of ATiO{sub 3}–Pr thin films prepared by a photochemical method (where A = Ba and Ca)

Highlights: • A method of photochemical deposition has been used to the preparation of (Ba,Ca)TiO{sub 3} thin films doped Pr(III). • The (Ba,Ca)TiO{sub 3}/Pr(III) films under 375 nm excitation shows emissions attributable to {sup 1}D{sub 2} → {sup 3}H{sub 4} transition of Pr ion. • These PL signals decreased above 10 mol% of Pr(III). • Analysis suggests the presence of intermediate energy levels in the band gap influences in the PL processes. - Abstract: This article reports the characterization and optical properties of (Ba,Ca)TiO{sub 3} thin films doped with Pr at different proportions (0–15 mol%). The films were deposited on Si (1 0 0) and quartz substrates using a photochemical method and post-annealed at 900 °C. The evaluation of photo-reactivity of the precursor complexes was monitored by UV–vis and FT-IR spectroscopy. The obtained films were characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The results indicate that Ba, Ca, Ti, O and Pr are present in the form of perovskite. Under UV light excitation (375 nm) the (Ba,Ca)TiO{sub 3}–Pr films show the characteristic emissions ascribed to {sup 1}D{sub 2} → {sup 3}H{sub 4} transition of Pr{sup 3+} ion. The optical measurements show the presence of intermediate energy levels in the band gap which influence the emission processes.

36 MATERIALS SCIENCE↗

Electrical characterization of grain boundaries of CZTS thin films using conductive atomic force microscopy techniques

Graphical abstract: Experimental setup for conducting AFM (C-AFM). - Highlights: • Cu{sub 2}ZnSnS{sub 4} (CZTS) thin film was grown by reactive co-sputtering. • The electronic properties were probed using conducting atomic force microscope, scanning Kelvin probe microscopy and scanning capacitance microscopy. • C-AFM current flow mainly through grain boundaries rather than grain interiors. • SKPM indicated higher potential along the GBs compared to grain interiors. • The SCM explains that charge separation takes place at the interface of grain and grain boundary. - Abstract: Electrical characterization of grain boundaries (GB) of Cu-deficient CZTS (Copper Zinc Tin Sulfide) thin films was done using atomic force microscopic (AFM) techniques like Conductive atomic force microscopy (CAFM), Kelvin probe force microscopy (KPFM) and scanning capacitance microscopy (SCM). Absorbance spectroscopy was done for optical band gap calculations and Raman, XRD and EDS for structural and compositional characterization. Hall measurements were done for estimation of carrier mobility. CAFM and KPFM measurements showed that the currents flow mainly through grain boundaries (GB) rather than grain interiors. SCM results showed that charge separation mainly occurs at the interface of grain and grain boundaries and not all along the grain boundaries.

36 MATERIALS SCIENCE↗

Structural, XPS and magnetic studies of pulsed laser deposited Fe doped Eu{sub 2}O{sub 3} thin film

Highlights: • Growth of Fe doped Eu{sub 2}O{sub 3} thin films by PLD. • XRD and Raman’s spectroscopy used for structure confirmation. • The electronic states of Eu and Fe are confirmed by XPS. • Magnetic properties reveals room temperature magnetic ordering in deposited film. - Abstract: Fe (4 at.%) doped europium (III) oxide thin film was deposited on silicon (1 0 0) substrate by pulsed laser deposition technique. Structural, spectral and magnetic properties were studied by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and magnetization measurements. XRD and Raman spectroscopy reveal that the grown film is single phased and belongs to the cubic structure of Eu{sub 2}O{sub 3}. XPS study of the Eu{sub 1.92}Fe{sub 0.08}O{sub 3} film shows that Fe exists in Fe{sup 3+} ionic state in the film. The film exhibits magnetic ordering at room temperature.

36 MATERIALS SCIENCE↗

Thin sensing layer based on semi-conducting β-cyclodextrin rotaxane for toxic metals detection

Highlights: • Microwave-assisted synthesis of rotaxane based on anthracene and β-cyclodextrin. • Morphological and optical characterization of thin solid film. • Elaboration of impedimetric gold/rotaxane sensor. • Investigation of the membrane sensitivity towards Hg{sup 2+}, Cu{sup 2+} and Pb{sup 2+} cations. - Abstract: An impedimetric sensor based on a new semi-conducting rotaxane has been described for detection of toxic cations. The rotaxane, consists on a π-conjugated material encapsulated into β-cyclodextrin (β-CD); it has been synthesized via the Williamson reaction under microwaves irradiation. The supramolecular structure of the compound was confirmed by NMR and FT-IR spectroscopies. A thin solid film of the rotaxane was deposited by spin-coating to develop a new electrochemical sensor. The morphological properties of the organic membrane were evaluated using contact angle measurements and atomic force microscopy. The gold/rotaxane/solution interfaces were investigated by electrochemical impedance spectroscopy and the obtained data were fitted using an equivalent electrical circuit. The response of the gold/rotaxane membrane towards Hg{sup 2+}, Cu{sup 2+} and Pb{sup 2+} cations was studied and the results showed a good sensitivity to the mercury cations.

36 MATERIALS SCIENCE↗

A rapid and convenient method for the preparation of thermochromic VO{sub 2} thin films

Highlights: • A simple and efficient route has been developed for the preparation of VO{sub 2} thin films. • VO{sub 2} films annealed at high enough crystallization temperature were obtained and analyzed. • Excellent optical modulation both in the visible and near-infrared region has been achieved in the prepared VO{sub 2} film. - Abstract: The annealing temperature for the preparation of VO{sub 2} films with sputtering method have always been applied in the range of 300–500 °C. Herein, a simple and efficient route has been developed for the preparation of VO{sub 2} thin films through the thermal oxidation of sputtered vanadium film at 585 °C. Structural, morphological, elemental analysis and thermochromic properties of synthesized VO{sub 2} films are reported. Different from the traditional sputtered VO{sub 2} films, large change of transmittance has been found in the visible region during phase transition. The present work shows the feasibility to fabricate reliably reproduced high quality VO{sub 2} films with reversible phase transition and excellent optical modulation both in the visible and near-infrared region.

36 MATERIALS SCIENCE↗

Structural, optical and femtosecond third-order nonlinear optical properties of LiNbO{sub 3} thin films

Highlights: • Fs third order NLO properties of LiNbO{sub 3} thin films were investigated. • Al:ZnO was used as a buffer layer to control the growth of LiNbO{sub 3}. • The magnitude of the χ{sup (3)} of all films was ∼10{sup −11} e.s.u. • χ{sup (3)} obtained here is much higher that of single crystal Z-cut LiNbO{sub 3}. - Abstract: LiNbO{sub 3} thin films were deposited by means of Al:ZnO as intermediate layer using pulsed laser deposition and their structural, linear and nonlinear optical (NLO) properties were investigated. The films were found to be polycrystalline, (110) orientation for Al:ZnO/fused silica and (300) orientation for Al:ZnO/quartz substrates. The films demonstrated a transparency of >80% in the visible and near-infrared region. The NLO studies were performed with the Z-scan technique using ∼150 fs, 80 MHz pulses at 800 nm. The studies revealed that the polycrystalline LiNbO{sub 3}films and (300) LiNbO{sub 3}films demonstrated reverse saturable absorption while a transition to saturable absorption was observed in the case of (110) LiNbO{sub 3}. The presence of two-photon absorption is attributed to the indirect transition via intermediate defect levels which is related to the structural asymmetry. The large nonlinearity in refractive index could be a result of the strain induced ferroelectric polarization. The magnitude of the third order optical nonlinearity of all films was ∼10{sup −11} e.s.u. which is orders of magnitude higher than the value obtained for single crystal Z-cut LiNbO{sub 3}.

36 MATERIALS SCIENCE↗

Screen printing large-area organometal halide perovskite thin films for efficient photodetectors

Highlights: • A stable paste with perovskite precursor was produced out. • Screen printing was proposed to fabricate perovskite thin films. • The perovskite photodetectors with symmetric architectures show reasonable performance with high photocurrent and fast response. - Abstract: Organometal halide perovskites have demonstrated excellent features compared to conventional optoelectronic materials. To date, the perovskite films have generally been fabricated by either spin coating or vapor deposition. However, both methods cannot simultaneously meet large scale and low cost of production. Here, a simple, low-cost and high-throughput strategy was proposed to fabricate perovskite thin films, which were further applied in photodetectors. First, lead compound nanoparticles were synthesized by a solvent precipitation method, then a paste with the lead compound nanoparticles was screen printed to form PbO films involving calcination, and next the PbO films directly reacted with CH{sub 3}NH{sub 3}I solution to convert into CH{sub 3}NH{sub 3}PbI{sub 3} films. The CH{sub 3}NH{sub 3}PbI{sub 3} films consisted of micron crystals, whose sizes can be effectively controlled by adjusting CH{sub 3}NH{sub 3}I concentration. Furthermore, the CH{sub 3}NH{sub 3}PbI{sub 3} films were applied in photodetectors, which showed good performance with high sensitivity and fast response.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Cost-effective fabrication of (g-C3N4 + Mo) added photostable ZnO thin films for enhanced visible light responsive photocatalytic dye degradation

Highlights: • First report on ZnO:Mo/GCN films prepared by simple cost-effective jet nebulizer spray method for dye degradation. • A remarkable enhancement in the photocatalytic dye degradation efficiency is achieved for ZnO. • The mechanism for the enhanced degradation is explained on the basis of the obtained point of zero charge values. • Optical, PL, SEM and XPS studies support the discussion on the photocatalytic property of ZnO:Mo/GCN. - Abstract: The photocatalytic activity of ZnO:Mo/GCN (ZnO:Molybdenum/g-C{sub 3}N{sub 4}) thin films deposited using a simple cost-effective jet nebulizer spray pyrolysis technique with different Mo doping concentrations (1,2 and 3 at.%) was studied. The photocatalytic degradation test was carried out against Methylene blue (MB) and Rhodamine B (RhB) dyes under visible light. It is found that thin film of ZnO:Mo/GCN with 1 at.% of Mo exhibits superior photocatalytic efficiency compared with the other samples. The degradation rate constant of this sample is 0.0727 and 0.0268 min{sup −1} for the tested MB and RhB dyes, respectively which are nearly two times and four times greater than the respective rate constant values of pristine ZnO. The mechanism involved in the enhanced photocatalytic activity is addressed with the help of obtained results. The properties of the deposited samples are correlated appropriately with the photocatalytic efficiency of the samples. The photostability of the prepared catalysts is tested experimentally.

36 MATERIALS SCIENCE↗

Annealing influence on the magnetostructural transition in Gd 5 Si 1.3 Ge 2.7 thin films

Due to the emerging cooling possibilities at the micro and nanoscale, such as the fast heat exchange rate, the effort to synthesize and optimize the magnetocaloric materials at these scales is rapidly growing. Here, we report the effect of different thermal treatments on Gd 5 Si 1.3 Ge 2.7 thin film in order to evaluate the correlation between the crystal structure, magnetic phase transition and magnetocaloric effect. For annealing temperatures higher than 500ºC, the samples showed a typical paramagnetic behavior. On the other hand, thermal treatments below 500ºC promoted the suppression of the magnetostructural transition at 190 K, while the magnetic transition around 249 K is not affected. This magnetostructural transition extinction was reflected in the magnetocaloric behavior and resulted in a drastic decrease in the entropy change peak value (of about 68%). An increase in T C was reported, proving that at the nanoscale, heat treatments may be a useful tool to optimize the magnetocaloric properties in Gd 5 (Si x Ge 1-x ) 4 thin films.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Sulvanite (Cu 3 VS 4 ) nanocrystals for printable thin film photovoltaics

Copper Vanadium Sulfide (Cu 3 VS 4 ), also known as sulvanite, has recently emerged as a suitable absorber material for thin film photovoltaics. The synthesis of Cu 3 VS 4 nanocrystals via a rapid solvothermal route is reported for the first time. The phase purity of the Cu 3 VS 4 nanocrystals has been confirmed by X-ray powder diffraction (XRD) and Raman spectroscopy, while the nanoparticle size, of about 10 nm, was evaluated by transmission electron microscopy (TEM). Successful ligand exchange with sulfide, an inorganic ligand, demonstrated that the nanoparticles are amenable to surface modifications, key element in solution processing. Further annealing of as-synthesized nanocrystals under a sulfur/argon atmosphere at 600 °C, rendered highly crystalline Cu 3 VS 4 powders exhibiting an impurity that could be potentially mitigated by annealing temperature optimization. Furthermore, Cu 3 VS 4 , formed solely from Earth-abundant elements, could provide an inexpensive, reliable approach to fabricating solution processed thin film photovoltaic absorbers.

36 MATERIALS SCIENCE↗

Investigation of synchrotron X-ray induced oxidation of Ag–Cu thin-film

Combinatorial Ag-Cu thin-films were irradiated by synchrotron X-ray in air to investigate the beam damage on the surface of the thin-film. The main effect was found to be oxidation with the oxidation state primarily depending on film composition: CuO formed on the pure Cu film, whereas Cu 2 O formed in the presence of Ag. Meanwhile, formation of crystalline Ag 2 O 2 was favored and preferentially in the Ag-rich area. Lastly, these results are of great importance in studying the oxidation of noble metal nano-film, and in the characterization of nano-films using synchrotron X-ray.

36 MATERIALS SCIENCE↗

Thin-film composite membranes based on hyperbranched poly(ethylene oxide) for CO 2 /N 2 separation

Cross-linked amorphous poly(ethylene oxide) (XLPEO) is one of the leading membrane materials for post-combustion CO 2 capture. For example, XLPEO prepared from poly(ethylene glycol) methyl ether acrylate (PEGMEA) exhibited CO 2 permeability of 570 Barrer and CO 2 /N 2 selectivity of 41 at 35 °C. However, these XLPEOs cannot be dissolved in coating solutions, making it impossible to be fabricated into thin-film composite (TFC) membranes using state-of-the-art manufacturing processes. In this study, we synthesized high molecular weight yet soluble HPEO via atom transfer radical polymerization (ATRP). These polymers were thoroughly characterized and compared with XLPEO, including thermal transitions, free volumes, and pure-gas sorption and permeation properties. A polymer with the best combination of CO 2 permeability (540 Barrer) and CO 2 /N 2 selectivity (43) was fabricated into defect-free TFC membranes with a thickness as thin as 506 ± 44 nm. When challenged with simulated flue gas containing water vapor at 35 °C for over 100 h, the membrane shows stable CO 2 permeance of 850 GPU and CO 2 /N 2 selectivity of 37, comparable to the leading commercial membranes for carbon capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗